DK165751B - SILICONE-CONTAINING HIGH OXYGEN PERMEABILITY POLYMERS AND PROCEDURES FOR PRODUCING THEREOF - Google Patents

Abstract

Clear, strong, crosslinked polymers are described, which are obtained by copolymerization of (A) 8-70% of a linear or branched polysiloxane of 400-100,000 molecular weight (MW) containing at least two terminal or pendant, polymerizable, vinyl groups per each 5000 MW unit of polysiloxane and which are attached to the polysiloxane through at least two urethane, thiourethane, urea or amide linkages and (B) 30-92% of a mono- or divinyl compound or a mixture of such monomers consisting of 85 to 100% of water insoluble monomers. These polymers are useful in the preparation of hard or soft contact lenses.

Description

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Den foreliggende opfindelse angår klare, stærke, tværbundne polymerer, der er fremkommet ved copolymerisation af (A) en lineær eller forgrenet polysiloxanmakromer indeholdende mindst to endestillede eller sidestillede, polymeriser- 5 bare vinylgrupper, der er bundet til polysiloxanen gennem en urethan-, thiourethan-, urinstof- eller amidgruppe, og (B) en vinyl- eller divinylmonomer eller blandinger af monomerer, hvor monomererne består af 85-100% vanduopløselige monomerer samt en fremgangsmåde til fremstilling deraf. De om- 10 handlede tværbundne polymerer er nyttige ved fremstillingen af bløde eller hårde kontaktlinser, især de hårde linser.The present invention relates to clear, strong, crosslinked polymers obtained by copolymerization of (A) a linear or branched polysiloxane macromer containing at least two terminal or parallel polymerizable vinyl groups attached to the polysiloxane through a urethane, thiourethane polymer. , (U) a urea or amide group, and (B) a vinyl or divinyl monomer or mixtures of monomers, wherein the monomers consist of 85-100% water-insoluble monomers and a process for their preparation. The cross-linked polymers referred to are useful in the preparation of soft or hard contact lenses, especially the hard lenses.

Kontaktlinser falder inden for to hovedkategorier, normalt kaldet "hårde" og "bløde", men det er bedre at skelne 15 mellem de to typer ved hjælp af den måde, hvorpå de er anbragt på øjet. Hårde linser er temmeligt løst anbragt for at lette tårevæskeudveksling mellem linse og hornhinde. De gør dette ved deres "gyngestol"-bevægelse, hvorved de kontinuerligt pumper tårevæske ud fra mellemrummet mellem linse og øjen-20 overflade. En sådan tårevæskeudveksling er den eneste måde, hvorpå alt vigtigt oxygen tilføres til hornhinden hos brugerne af konventionelle hårde kontaktlinser, der er fremstillet ud fra polymethylmethacrylat (PMMA). Selv om hårde PMMA-linser - i det mindste i begyndelsen - er ubehagelige og irrite-25 rende for brugeren, fordi det blinkende øjenlåg rammer en hård kant, er de ikke desto mindre populære, fordi de kan fremstilles med stor præcision ved drejning og slibning. Dette er særlig betydningsfuldt for korrigeringen af bygningsfejl med linser af asymmetrisk udformning. Det er en anden 30 fordel, at de er meget lette at holde rene, idet de ikke kræver sterilisering.Contact lenses fall into two main categories, usually called "hard" and "soft," but it is better to distinguish 15 between the two types by the way they are applied to the eye. Hard lenses are rather loosely arranged to facilitate tear fluid exchange between lens and cornea. They do this by their "rocking chair" movement, thereby continuously pumping tear fluid from the gap between lens and eye-surface. Such tear fluid exchange is the only way in which all important oxygen is supplied to the cornea of users of conventional hard contact lenses made from polymethyl methacrylate (PMMA). Although hard PMMA lenses - at least initially - are unpleasant and irritating to the user because the flashing eyelid hits a hard edge, they are nevertheless popular because they can be manufactured with great precision in turning and grinding. . This is particularly important for the correction of building defects with asymmetric lenses. Another advantage is that they are very easy to keep clean as they do not require sterilization.

På den anden side klæber bløde kontaktlinser tæt til hornhinden, og de er derfor meget behageligere for brugeren.On the other hand, soft contact lenses adhere tightly to the cornea and are therefore much more comfortable for the user.

35 Eftersom de kun tillader en begrænset tårevæskeudveksling, skal de have en tilstrækkelig høj oxygenpermeabilitet til at forhindre beskadigelse af øjet, selv om de bæres uafbrudt 235 Since they allow only limited tear fluid exchange, they must have a sufficiently high oxygen permeability to prevent eye damage, even if they are worn continuously 2

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i adskillige timer. I alle handelsgængse, bløde linser er denne (^-permeabilitet en funktion af deres vandindhold, dvs. deres hydrogel-beskaffenhed. Desuden virker vand som en blødgører, der giver linsen dens blødhed og den nødven-5 dige hydrofile beskaffenhed, som tillader den at svømme og rotere på hornhinden i stedet for at klæbe til denne. Klæbning til hornhinden er hovedproblemet ved hydrofobe, bløde linser, f.eks. de ellers meget attraktive silicone-kautsjuklinser. Selv om bløde hydrogel-linser repræsenterer et frem-10 skridt med hensyn til behagelighed, er præcisionen bragt i fare, eftersom en vis mængde forvridning på grund af vand-kvældning er uundgåelig. Fordi de er tilbøjelige til at rotere på øjet, er bygningsfejl også et meget vanskeligere problem at løse. Desuden giver proteinadsorption og desin-15 fektion anledning til store betænkeligheder, og stigningen i behagelighed er i stor udstrækning opvejet af den større ulejlighed ved mere sofistikerede linseplejeprocedurer.for several hours. In all commercially available soft lenses, this permeability is a function of their water content, i.e., their hydrogel nature. In addition, water acts as a plasticizer to give the lens its softness and the necessary hydrophilic nature which allows it to swimming and rotating on the cornea instead of adhering to it.Adhesion to the cornea is the main problem with hydrophobic soft lenses, such as the otherwise very attractive silicone rubber lenses.Although soft hydrogel lenses represent an advance in terms of for convenience, precision is jeopardized as a certain amount of distortion due to water swelling is unavoidable because they tend to rotate on the eye, building defects are also a much more difficult problem to solve. fection causes major concerns, and the increase in comfort is largely offset by the greater inconvenience of more sophisticated lens care procedures is.

Den næste betydningsfulde udvikling inden for kontaktlinse--teknologien var fremstillingen af linser, der kan bæres 20 kontinuerligt, dag og nat, i op til flere uger. Linsens oxy-genpermeabilitet skal forøges mange gange til dette formål, fordi alt oxygenet i tilstanden med lukkede øjne under søvnen tilføres til hornhinden fra det blodgennemstrømmede øjenlåg. Blandt de mange forsøg, der ikke er lykkedes tilfreds-25 stillende i denne henseende,kan nævnes: (1) hydrogeler med et højt vandindhold på op til 70% vand, ulempen ved disse er mekanisk svaghed, hvorfor de skal gøres tykkere, og 02-permeabiliteten følgelig reduceres; og (2) silicone-kaut-sjuklinser, der konsekvent har slået fejl på grund af deres 30 ekstreme hydrofobe beskaffenhed, de klæber som en sugekop til hornhinden og har ført til alvorlige øjenskader. Forsøg på at gøre silicone-kautsjuklinsers overflade tilstrækkelig hydrofil til at forhindre dette har ikke givet overdrevent gode resultater, hovedsageligt fordi den behandlede overflade-35 region er for tynd til at være permanent. De linser, der fremstilles af Dow Corning under handelsnavnene "SILCON" og 3The next significant advancement in contact lens technology was the manufacture of lenses that can be worn continuously, day and night, for up to several weeks. The oxy gene permeability of the lens must be increased many times for this purpose because all the oxygen in the closed-eye condition during sleep is supplied to the cornea from the blood-flowing eyelid. Among the many unsuccessful experiments in this regard are: (1) hydrogels with a high water content of up to 70% water, the disadvantage of which is mechanical weakness, which is why they need to be thickened, and 02 consequently, the permeability is reduced; and (2) silicone cautious lenses that have consistently failed due to their extreme hydrophobic nature, they adhere like a suction cup to the cornea and have led to serious eye damage. Attempts to make the surface of silicone rubber lenses sufficiently hydrophilic to prevent this have not produced excessively good results, mainly because the treated surface region is too thin to be permanent. The lenses manufactured by Dow Corning under the trade names "SILCON" and 3

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"SILSOFT", behandles f.eks. tildannelse af et -Si-OH-overfladelag, der imidlertid er så tyndt, at det let slides af, især på en hård linse. Det er et formål med den foreliggende opfindelse at tilvejebringe en siliconeholdig hård linse, 5 hvis overflade permanent kan fugtes. En anden ulempe ved 100% siliconekautsjuk-kontaktlinser er, at det er vanskeligt at afslutte og slibe kanterne og derved gøre dem behagelige for brugeren. Dette er uløseligt forbundet med alt for kautsjukagtige materialer. Det er et yderligere 10 formål med den foreliggende opfindelse at tilvejebringe siliconeholdige polymere materialer, der strækker sig fra "bløde" til "hårde" - for at bruge kontaktlinse-terminologien - men som alle let kan slibes."SILSOFT", e.g. forming a -Si-OH surface layer, however, which is so thin that it easily wears off, especially on a hard lens. It is an object of the present invention to provide a silicone-containing hard lens whose surface can be permanently wetted. Another disadvantage of 100% silicone rubber contact lenses is that it is difficult to finish and grind the edges, thereby making them comfortable for the user. This is inextricably linked to overly rubbery materials. It is a further object of the present invention to provide silicone-containing polymeric materials ranging from "soft" to "hard" - to use the contact lens terminology - but all of which can be easily sanded.

Nyere eksempler på siliconeholdige, hydrofobe polymerer er 15 beskrevet i US-PS nr. 4.153.641, 4.189.546 og 4.195.030, og de består af polymeriserede eller copolymeriserede poly-siloxan- eller polyparaffinsiloxandiacrylater og -methacry-later med høj molekylvægt. De fremkomne polymerer er hydrofobe. I US-PS nr. 4.217.038 er der beskrevet en overflade-20 behandling for at gøre deres overflade hydrofil. Andre poly-siloxanholdige kontaktlinsematerialer er beskrevet i US-PS nr. 4.208.362, 4.208.506, 4.254.248, 4.259.467, 4.277.595, 4.260.725 og 4.276.402. Alle disse patenter er baseret på bis-methacrylatestere af lineære polysiloxandioler. På 25 grund af deres bløde beskaffenhed er lineære polysiloxaner ikke egnede til fremstilling af de hårde, stive materialer, der er nødvendige for en hård kontaktlinse. I US-PS nr. 4.136.250 er der udover ovennævnte bis-methacrylater af lineære polysiloxandioler også beskrevet bis- og tris-30 -methacrylater af dioler og trioler, hvor de funktionelle grupper er sidestillede, ikke endestillede, til hovedpoly-siloxankæden, og derudover forbindelser, der er forbundet med polysiloxanen via bis-urethanbindinger. Alle sammensætningerne er imidlertid hydrogeler og som sådanne kun egnede 35 til bløde kontaktlinser.More recent examples of silicone-containing hydrophobic polymers are described in U.S. Patent Nos. 4,153,641, 4,189,546 and 4,195,030, and they consist of polymerized or copolymerized high-molecular weight polysiloxane or polyparaffin siloxane diacrylates. The resulting polymers are hydrophobic. U.S. Patent No. 4,217,038 discloses a surface treatment to render their surface hydrophilic. Other poly-siloxane-containing contact lens materials are disclosed in U.S. Patent Nos. 4,208,362, 4,208,506, 4,254,248, 4,259,467, 4,277,595, 4,260,725, and 4,276,402. All of these patents are based on bis-methacrylate esters of linear polysiloxane diols. Due to their soft nature, linear polysiloxanes are not suitable for producing the hard, rigid materials needed for a hard contact lens. In U.S. Patent No. 4,136,250, in addition to the above-mentioned bis-methacrylates of linear polysiloxane diols, bis and tris-30 methacrylates of diols and triols are disclosed, wherein the functional groups are parallel, not terminal, to the main polysiloxane chain, and in addition, compounds that are connected to the polysiloxane via bis-urethane bonds. However, all the compositions are hydrogels and as such are only suitable for soft contact lenses.

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En stiv, siliconeholdig, hård lirise er beskrevet i US-PS nr. 4.152.508. Den består af en copolymer af et oligosil-oxanylalkylacrylat med forskellige comonomerer, såsom di-methylitaconat og methylmethacrylat. Selv om der påberåbes 3 c ...... soen m“10 cm (STP).cm .A rigid, silicone-containing, hard lyric is disclosed in U.S. Patent No. 4,152,508. It consists of a copolymer of an oligosiloxanyl alkyl acrylate with various comonomers such as dimethyl etaconate and methyl methacrylate. Even though 3 c ...... the sow m “10 cm (STP) .cm.

5 oxygenpermeabiliteter på 3-50 x 10 —^- · 9&r cm sek.cm.Hg de store mængder oligosiloxansubstitueret methaerylat (>40%), der er nødvendige for at få C^-permeabiliteter på over 9, samtidigt polymeren for blød til at kunne anvendes som en hård linse. Kun hvis Si-monomeren udgør mindre end 25% af 10 polymeren, er polymerhårdheden tilstrækkelig høj til anvendelse som hård kontaktlinse. Eftersom siloxanindholdet også påvirker befugteligheden i ugunstig retning, er det selvfølgeligt fordelagtigt kun at skulle anvende den mindst mulige mængde Si i polymeren, netop tilstrækkeligt til at op-15 nå den nødvendige 02-permeabilitet.5 oxygen permeabilities of 3-50 x 10 10 - · 9 & r cm sec.cm.Hg the large amounts of oligosiloxane-substituted methaerylate (> 40%) needed to obtain C ^ permeabilities in excess of 9, at the same time as the polymer too soft to could be used as a hard lens. Only if the Si monomer constitutes less than 25% of the polymer will the polymer hardness be sufficiently high for use as a hard contact lens. Of course, since the siloxane content also adversely affects wettability, it is advantageous to use only the least amount of Si in the polymer, just enough to achieve the required O 2 permeability.

Siloxanurethanacrylatforbindelser, der kan anvendes ved fremstillingen af overtræksmaterialer til strålingshærdning, er beskrevet i US-PS nr. 4.130.708. Disse siloxan-urethanacrylatforbindelser kan blandes med andre bestand-20 dele, der normalt forefindes i overtræksmaterialer, og strålingshærdes med ultraviolet lys. Anvendelsen af sådanne materialer til kontaktlinser er hverken beskrevet eller foreslået i dette patentskrift. De i dette patentskrift beskrevne overtræksmaterialer indbefatter ikke nogen hydro-25 file monomerkomponenter.Siloxane urethane acrylate compounds which can be used in the preparation of radiation cure coating materials are described in U.S. Patent No. 4,130,708. These siloxane-urethane acrylate compounds can be mixed with other constituents normally present in coating materials and radiated by ultraviolet light. The use of such contact lens materials is neither described nor proposed in this patent. The coating materials described in this patent do not include any hydrophilic monomer components.

Også i GB-PS nr. 2.067.213 er der beskrevet siloxanurethan-acrylatforbindelser, der kan anvendes ved fremstillingen af fotohærdelige overtræksmaterialer. Anvendelsen af sådanne materialer til kontaktlinser er ikke beskrevet. De i dette 30 patentskrift beskrevne overtræksmaterialer indbefatter ikke nogen hydrofile monomerkomponenter og heller ikke de her omhandlede hydrofobe comonomerer.Also in GB-PS No. 2,067,213 siloxane urethane acrylate compounds are disclosed which can be used in the preparation of photo-curable coating materials. The use of such materials for contact lenses is not described. The coating materials described in this patent do not include any hydrophilic monomer components, nor do the hydrophobic comonomers disclosed herein.

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Fra US-patentskrift nr. 4.341.889 kendes tværbundne polymerer bestående af a) polysiloxaner med polymeriserbare endestillede grupper, b) tert-butylstyren og c) hydrofile vinylmonomerer. Polysiloxanerne a) indeholder en bivalent gruppe R, som forbinder siliciumatomet med de polymeriser-bare endestillede grupper, og som kun kan betyde alkylen eller arylen. I US-patentskrift nr. 4.341.889 omtales overhovedet ikke anvendelse af diisocyanat, som er et væsentligt aspekt af den foreliggende opfindelse.U.S. Patent No. 4,341,889 discloses cross-linked polymers consisting of a) polysiloxanes with polymerizable end groups, b) tert-butyl styrene, and c) hydrophilic vinyl monomers. The polysiloxanes a) contain a bivalent group R which connects the silicon atom to the polymerizable terminal groups and which can only mean alkylene or aryl. U.S. Patent No. 4,341,889 does not disclose at all the use of diisocyanate, which is an essential aspect of the present invention.

Det er kendt, at SiOiCH^^ er en mere effektiv oxygen-overfører, hvis det er til stede i form af siloxanpolymer, end hvis det kun er en del af en sidegruppe med lav molekylvægt.It is known that SiO 2 CH 2 is a more efficient oxygen transmitter if present in the form of siloxane polymer than if it is only part of a low molecular weight side group.

De lange polysiloxankæder, der er til stede i materialerne 15 ifølge US-PS nr. 4.153.641 og dermed beslægtede patenter, reducerer imidlertid stivheden drastisk, hvilket fører til kautsjukagtige og bløde materialer. Desuden er deres forenelighed med sådanne ubeslægtede polymerer som polymeth-acrylater ringe, og faseadskillelse, som er typisk for blandinger af polymerer med høj molekylvægt, fører til mere eller mindre opake produkter.However, the long polysiloxane chains present in the materials 15 of U.S. Patent No. 4,153,641 and related patents drastically reduce the rigidity leading to rubbery and soft materials. Furthermore, their compatibility with such unrelated polymers as polymethacrylates is poor, and phase separation, which is typical of mixtures of high molecular weight polymers, leads to more or less opaque products.

Det har nu overraskende vist sig, at hvis polyfunktionelle ^ polysiloxaner med høj molekylvægt, hvis ækvivalentvægt ikke er større end 5000, og som er bundet til mindst to endestillede eller sidestillede, polymeriserbare vinylgrupper gennem bis-urethanbindinger, inkorporeres i en tværbundet vinylcopolymer, opnås hårde, stive og klare produkter, der har fortrinlig (^-permeabilitet, op til fire gange større end det bedste kendte materiale, og som endog ved et sil-oxanindhold på >50% er tilstrækkeligt stive til at opfylde kravene til en hård kontaktlinse. Det har endvidere meget overraskende vist sig, at de her omhandlede siloxanholdige gg polymerer kan fremstilles med bedre befugtelighed end konventionelle hårde linser af PMMA, til trods for deres høje polysiloxanindhold.Surprisingly, it has now been found that if high-molecular-weight polyfunctional polysiloxanes, the equivalent weight of which is not greater than 5000, and which are bound to at least two terminated or juxtaposed polymerizable vinyl groups through bis-urethane bonds, are incorporated into a cross-linked vinyl copolymer, , rigid and clear products having excellent (^ permeability up to four times greater than the best known material, and which even at a siloxane content of> 50% are sufficiently rigid to meet the requirements of a hard contact lens. Furthermore, very surprisingly, it has been found that the siloxane-containing gg polymers in question can be made with better wettability than conventional hard lenses of PMMA, despite their high polysiloxane content.

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De foretrukne polysiloxanmakromerer til syntesen af hårde kontaktlinse-materialer er sådanne, som indeholder (a) mindst én urethanbindingsgruppe pr. 12 /SiO(CHg)2_/-en-heder, (b) mindst to polymeriserbare vinylgrupper, der er 5 bundet i sidestilling til polysiloxanhovedkæden og derfor indeholder mindst to endestillede /Si(CH^)-enheder, og (c) urethangrupper, der er afledt af voluminøse, cycloali-phatiske diisocyanater. De foretrukne comonomerer til kombination med polysiloxanmakromererne er acrylater og meth-10 acrylater, der, når de polymeriseres med sig selv, giver hårde homopolymerer med en høj glasovergangstemperatur, såsom methylmethacrylat, isopropyl-, isobutyl-, tert.butyl-, cyclohexyl- eller isobornylmethacrylat.The preferred polysiloxane macromers for the synthesis of hard contact lens materials are those containing (a) at least one urethane bond group per (B) at least two polymerizable vinyl groups which are in juxtaposition to the polysiloxane main chain and therefore contain at least two terminal / Si (CH 2) units, and (c) urethane groups, derived from bulky cycloaliphatic diisocyanates. The preferred comonomers for combination with the polysiloxane macromers are acrylates and methacrylates which, when polymerized by themselves, yield hard homopolymers with a high glass transition temperature such as methyl methacrylate, isopropyl, isobutyl, tert.butyl, cyclohexylacetam or isobornyl .

15 Selv om den foreliggende opfindelse først og fremmest angår hårde kontaktlinse-materialer, har det vist sig, at der også kan fremstilles klare, stærke, men kautsjukagtige polymerer. Sådanne polymerer, der er nyttige til mange forskelligartede anvendelser, såsom bio-forenelige implantanter, 20 bandager til sårbehandling eller som bløde kontaktlinser, er således et andet aspekt af den foreliggende opfindelse. I overensstemmelse hermed ligger det inden for den foreliggende opfindelses rammer at anvende comonomerer, der resulterer i stærke, men fleksible og kautsjukagtige poly-25 merer.Although the present invention is primarily concerned with hard contact lens materials, it has been found that clear, strong but rubbery polymers can also be produced. Thus, such polymers useful for many diverse applications, such as biocompatible implants, wound dressings or as soft contact lenses, are another aspect of the present invention. Accordingly, it is within the scope of the present invention to use comonomers which result in strong but flexible and rubbery polymers.

Polymeren ifølge den foreliggende opfindelse er ejendommelig ved, at den består af et tværbundet polymerisationsprodukt af 30 A) fra 15 til 60 vægt-% af en lineær eller forgrenet polysiloxanmakromer med en molekylvægt fra 400 til 100.000, målt ved endegruppeanalyse eller gelpermeationskromatografi, hvilken makromer indeholder mindst to endestillede eller sidestillede polymeriserbare olefiniske grupper for hver 35 5000 molekylvægtsenheder polysiloxan, idet grupperne er bundet til polysiloxanen med mindst to urethan-, thioure- s 7The polymer of the present invention is characterized in that it consists of a crosslinked polymerization product of 30 A) from 15 to 60% by weight of a linear or branched polysiloxane macromer having a molecular weight of 400 to 100,000, as measured by end group analysis or gel permeation chromatography, which contains macromers. at least two terminal or parallel polymerizable olefinic groups for each 35,000 molecular weight units of polysiloxane, the groups being bonded to the polysiloxane with at least two urethane, thioureas 7

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than-, urinstof- eller amidbindinger, og idet makromeren har strukturen 5 1 Y—X—Rj--SiO---SiO--jiO Si—Ri~X—Y (Ai) -k r IA J*2 1° . Y yi eller 15 20 <R2>3—Si°--jiO-----|i0---Si(Rz) 3 (A2)than the, urea or amide bonds, and the macromer having the structure 5 1 Y - X - R 1 - SiO --- SiO - 1 SiO - R 1 ~ X - Y (A 1) -k r IA J * 2 1 °. Y yi or <R2> 3 — Si ° --jiO ----- | i0 --- Si (Rz) 3 (A2)

Λ JX1 Γ ' j LΛ JX1 Γ 'j L

yz + i 25 hvori er en lineær eller forgrenet alkylengruppe med 2-6 carbonatoraer eller en polyoxyalkylengruppe med strukturen CH2CHO] nCH2CH- (G) 30 R3 R3 hvori R3 er hydrogen eller methyl, og n er et helt tal på 1—50, R2, **d' ^f/ ^g» ^h' ^i* ^k 35 methyl, Xi og x2 er hele tal fra 1 til 500, med det forbehold, at summen af Χχ + x2 er 7 til 1000, y-L er 0 til 14, og y2 er 1 til 13, med det forbehold, at forholdet 5 8yz + i 25 wherein is a linear or branched alkylene group having 2-6 carbon atoms or a polyoxyalkylene group having the structure CH2CHO] nCH2CH- (G) R3 R3 wherein R3 is hydrogen or methyl and n is an integer of 1-50, R2 , ** d '^ f / ^ g »^ h' ^ i * ^ k 35 methyl, Xi and x2 are whole numbers from 1 to 500, with the proviso that the sum of Χχ + x2 is 7 to 1000, yL is 0 to 14, and y2 is 1 to 13, with the proviso that the ratio 5 8

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X1 + x2 X1 + x2 _ eller _ ikke er større end 70,X1 + x2 X1 + x2 _ or _ is not greater than 70,

Yl + 2 Y2 + 1 X er et diradikal med formlen -Z1-CO-NH-R4-NH-CO- (C) 10 hvori Zi betyder oxygen, svovl eller NR5, og R5 er hydrogen eller C(1-4)-alkyl, Z-^ er forbundet med og R4 er det divalente radikal dannet ved fjernelse af NCO-grupperne fra et aliphatisk eller cycloaliphatisk diisocyanat, Y er en gruppe med formlen 15 -Z2-R8-Z2-CO-C=CH (D) r3 r6 20 -Z2-CH2-c=~=ch2 (E) eller r3 25 -0-R7-0-CH=CH2 (F) hvori Rg er hydrogen, methyl eller -COOR5, hvori R5 er hydrogen eller C(1-4)-alkyl, Z2 er oxygen eller -NR5-, R7 og Rg 30 er lineært eller forgrenet alkylen med 2-10 carbonatomer, og fra 85 til 40 vægt-% af en vinylmonomer (B) bestående af en blanding af en vandopløselig monomer B2 og en vanduopløselig monomer B^, eller en vand-uopløselig monomer B]^ eller en blanding deraf, idet monome-35 rerne er monoolefiniske, eller en diolefinisk monomer Bx eller en blanding deraf, eller en blanding af de monoolefiniske og diolefiniske monomerer med fra 85 til 100 vægt-% af de totale monomerer som vanduopløselige, hvor de monoolefiniske monomerer B^ er valgt blandt acrylater eller metha- 9Y1 + 2 Y2 + 1 X is a diradical of the formula -Z1-CO-NH-R4-NH-CO- (C) 10 wherein Z 1 is oxygen, sulfur or NR 5, and R 5 is hydrogen or C (1-4) - alkyl, Z- is linked to and R4 is the divalent radical formed by removal of the NCO groups from an aliphatic or cycloaliphatic diisocyanate, Y is a group of the formula 15 -Z2-R8-Z2-CO-C = CH (D) r3 r6 is -Z2-CH2-c = ~ = ch2 (E) or r3 is -O-R7-O-CH = CH2 (F) wherein Rg is hydrogen, methyl or -COOR5 wherein R5 is hydrogen or C (1) -4) alkyl, Z2 is oxygen or -NR5-, R7 and Rg30 are linear or branched alkylene of 2-10 carbon atoms and from 85 to 40% by weight of a vinyl monomer (B) consisting of a mixture of a water-soluble monomer B2 and a water-insoluble monomer B1, or a water-insoluble monomer B1, or a mixture thereof, the monomers being monoolefinic, or a diolefinic monomer Bx or a mixture thereof, or a mixture of the monoolefinic and diolefinic monomers with from 85 to 100% by weight of the total monomers r as water insoluble, wherein the monoolefinic monomers B 1 are selected from acrylates or metha.

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crylater med formlen CH2 =01*3000%2» acrylamider eller meth-acrylamider med formlen CH2=CR3CONH%2, maleater eller fuma-rater med formlen %20000Η=0Η000%2, itaconater med formlen R12OOCC(=CH2)CH2COOR12, vinylestere med formlen R12COOCH=CH2 5 eller vinylethere med formlen CH2=CHOR12, hvor R3 er hydrogen eller methyl, og R12 er en lineær eller forgrenet aliphatisk, cycloaliphatisk eller aromatisk alkylgruppe med 1-21 car-bonatomer, og som kan indeholde ether- eller thioether-bin-dinger eller en -CO-gruppe, eller er en heterocyclisk sub-10 stitueret alkylgruppe indeholdende oxygen-, svovl- eller nitrogenatomer, eller en polypropylenoxid- eller poly-n-butylenoxidgruppe med fra 2 til 50 alkoxygentagelsesenheder, eller betyder perfluorerede alkylgrupper med 1-12 carbonato-mer, eller er acylonitril, styren eller a-methylstyren, og 15 de olefiniske monomerer B2 er valgt blandt acrylater eller methacrylater med formlen CH2=CR3COORi3, acrylamider eller methacrylamider med formlen CH2=CR3CONHRi4 eller CH2=CR3CON(R5)2, maleater eller fumarater med formlen R13OCOCH=CHCOOR13, vinylethere med formlen CH2=CH0R13 eller 20 N-vinyllactamer, hvori R3 er hydrogen eller methyl, R5 er hydrogen eller C(1-4)-alkyl, R^3 er en carbonhydridgruppe med 1-10 carbonatomer substitueret med en eller flere vand-opløseliggørende carboxy-, hydroxy- eller tert-amino-grupper, eller en polyethylenoxidgruppe med 2-100 gentagelsesenheder, 25 og R24 har samme betydning som R13 eller R5, og de diolefi-niske monomerer Bx er valgt blandt acrylater eller methacrylater af allylalkohol, diacrylater eller dimethacrylater af ligekædet eller forgrenet alkylenglycol med 2-6 carbonatomer, af poly(ethylenoxid)glycol, af poly(propylenoxid)glycol, af 30 poly(n-butylenoxid)glycol, af thiodiethylenglycol, af neo-pentylenglycol, af trimethylolpropan, eller af pentaerythri-tol, eller reaktionsproduktet dannet ved omsætning af 1 mol af et di- eller tri-isocyanat med formlen OCN-R4-(NCO)v, hvori R4 har den ovenfor angivne betydning, og v er 1 eller 35 2, med 2 eller 3 mol af et hydroxyalkylacrylat eller -meth- acrylat.crylates of formula CH2 = 01 * 3000% 2 acrylamides or methacrylamides of formula CH2 = CR3CONH% 2, maleate or fumas of formula% 20000Η = 0.000% 2, itaconates of formula R12OOCC (= CH2) CH2COOR12, vinyl esters of or vinyl ethers of formula CH 2 = CHOR 12 wherein R 3 is hydrogen or methyl and R 12 is a linear or branched aliphatic, cycloaliphatic or aromatic alkyl group having 1-21 carbon atoms and which may contain ether or thioether substituents. bonds or a -CO group, or is a heterocyclic substituted alkyl group containing oxygen, sulfur or nitrogen atoms, or a polypropylene oxide or poly-n-butylene oxide group having from 2 to 50 alkoxy removal units, or meaning perfluorinated alkyl groups having 1-12 carbon atoms, or are acylonitrile, styrene or α-methylstyrene, and the olefinic monomers B2 are selected from acrylates or methacrylates of formula CH2 = CR3COORi3, acrylamides or methacrylamides of formula CH2 = CR3CONHRi 4 or CH2 = CR3CON (R5) 2, maleate or fumarates of formula R13OCOCH = CHCOOR13, vinyl ethers of formula CH2 = CHOR13 or N-vinyl lactams wherein R3 is hydrogen or methyl, R5 is hydrogen or C (1-4) alkyl R 3 is a hydrocarbon group having 1-10 carbon atoms substituted by one or more water-solubilizing carboxy, hydroxy or tert-amino groups, or a polyethylene oxide group having 2-100 repeating units, 25 and R 24 having the same meaning as R 13 or R5, and the diolefinic monomers Bx are selected from acrylates or methacrylates of allyl alcohol, diacrylates or dimethacrylates of straight or branched chain alkylene glycol of 2-6 carbon atoms, of poly (ethylene oxide) glycol, of poly (propylene oxide) glycol, of poly ( n-butylene oxide glycol, of thiodiethylene glycol, of neopentylene glycol, of trimethylolpropane, or of pentaerythritol, or the reaction product formed by reaction of 1 mole of a di- or tri-isocyanate of the formula OCN-R4- (NCO) v, wherein R4 has the above and v is 1 or 35 2, with 2 or 3 moles of a hydroxyalkyl acrylate or methacrylate.

1010

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Forbindelserne med strukturerne (Αχ) og (A2) er således polysiloxaner, der via en diisocyanatbinding er bundet til vinylgrupper, der kan være acryl- eller methacryl-, fumar-, 5 malein- eller itacongrupper (Y har formlen D), allylgrupper (Y har formlen E) eller vinylethergrupper (Y har formlen F).Thus, the compounds of structures (Αχ) and (A2) are polysiloxanes linked via a diisocyanate bond to vinyl groups which may be acrylic or methacrylic, fumaric, maleic or itacone groups (Y has the formula D), allyl groups (Y have the formula E) or vinyl ether groups (Y has the formula F).

Ved foretrukne udførelsesformer for den foreliggende opfindelse betyder alkylen med 3 eller 4 carbonatomer, og Χχ 10 + x2 er et tal fra 10 til 100, Yi er et tal fra 0 til 2, y2 er et tal fra 1 til 3, X betyder -Zx-CO-NH-R4-NH-CO-, hvor Ζχ betyder oxygen eller -NH-, R4 betyder diradikalet af et aliphatisk eller cycloaliphatisk diisocyanat med 6-10 carbonatomer, Y har formlen D, hvor Rg betyder hydrogen, Rg 15 betyder -CH2CH2-, og Z2 betyder oxygen eller -N- H3C-C-CH3In preferred embodiments of the present invention, alkylene has 3 or 4 carbon atoms, and Χχ 10 + x 2 is a number from 10 to 100, Y 1 is a number from 0 to 2, y 2 is a number from 1 to 3, X is -Zx -CO-NH-R 4 -NH-CO-, where Ζχ means oxygen or -NH-, R 4 means the diradical of an aliphatic or cycloaliphatic diisocyanate of 6-10 carbon atoms, Y has the formula D where Rg represents hydrogen, Rg 15 means - CH 2 CH 2 - and Z 2 represent oxygen or -N- H 3 C-C-CH 3

20 I20 I

ch3CH3

De mest foretrukne udførelsesformer omfatter polysiloxanen med strukturen (A2), hvor R4 betyder diradikalet af isopho-25 rondiisocyanat, Ζχ og Z2 betyder oxygen, og y2 er 1 eller 2.The most preferred embodiments include the polysiloxane of structure (A2), wherein R4 is the diradical of isophorodiisiisocyanate, Ζχ and Z2 are oxygen, and y2 is 1 or 2.

1111

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Blandt de anvendelige monomere kan nævnes: methyl-, ethyl-, propyl-, isopropyl-, butyl-, isobutyl-, tert.butyl-, ethoxy-ethyl-, methoxyethyl-, benzyl-, phenyl-, cyclohexyl-, tri-methylcyclohexyl-, isobornyl-, dicyclopentadienyl-, nor-5 bornylmethyl-, cyclododecyl-, 1,1,3,3-tetramethylbutyl-, n-butyl-, n-octyl-, 2-ethylhexyl-, decyl-, dodecyl-, tridecyl-, octadecyl-, glycidyl-, ethylthioethyl-, furfuryl-, hexafluor-isopropyl-, 1 ,1,2,2-tetrahydroperfluordodecyl-, tri-, tetra-eller pentasiloxanylpropylacrylater og -methacrylater samt 10 de tilsvarende amider, N-(1, 1-dimethyl-3-oxobutyl)-acryl- amid, mono- og dimethylfumarat, -maleat og -itaconat, diethyl-fumarat, isopropyl- og diisopropylfumarat og -itaconat, mono-og diphenyl- og methylphenylfumarat og -itaconat, methyl-vinylether og methoxyethylvinylether, vinylacetat, vinylprop-15 ionat, vinylbenzoat, acrylonitril, styren og a-methylstyren.Among the useful monomers include: methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, ethoxy-ethyl, methoxyethyl, benzyl, phenyl, cyclohexyl, trimethylcyclohexyl -, isobornyl, dicyclopentadienyl, norbornylmethyl, cyclododecyl, 1,1,3,3-tetramethylbutyl, n-butyl, n-octyl, 2-ethylhexyl, decyl, dodecyl, tridecyl -, octadecyl, glycidyl, ethylthioethyl, furfuryl, hexafluoro-isopropyl, 1, 1,2,2-tetrahydroperfluorododecyl, tri, tetra or pentasiloxanyl propyl acrylates and methacrylates and the corresponding amides, N- (1) , 1-dimethyl-3-oxobutyl) acrylamide, mono and dimethyl fumarate, maleate and itaconate, diethyl fumarate, isopropyl and diisopropyl fumarate and itaconate, mono and diphenyl and methylphenyl fumarate and methylacetate vinyl ether and methoxyethyl vinyl ether, vinyl acetate, vinyl propionate, vinyl benzoate, acrylonitrile, styrene and α-methyl styrene.

Til opnåelse af den høje klarhed, der er nødvendig til kontaktlinse-anvendelser, er det særlig nyttigt at anvende como-nomerer eller comonomerblandinger, hvis tilsvarende polymerer passer nøje sammen i opløselighedsparametre (δ) og/eller bryd-20 ningsindeks (RI) med værdierne for polydimethylsiloxan (6 = 15, RI = 1,43). Eksempler på sådanne monomerer er iso-bornylmethacrylat, tert.butylmethacrylat og blandinger af carbonhydridmethacrylater (RI 1,46) med fluorholdige monomerer, såsom hexafluorisopropylmethacrylat, trifluorethyl-25 methacrylat, 1,1,2,2-tetrahydroperfluroalkylmethacrylat eller 4-thia-6-perfluoralkylhexylmethacrylat, hvor alkyl er en car-bonkæde med 5-12 carbonatomer (RI-værdier på 1,38-1,40) (δ <15). Endvidere forbedrer perfluoralkylgruppeholdige monomerer polymerernes oxygenpermeabilitet stærkt på synergistisk 30 måde med polysiloxanen. De er derfor de særligt foretrukne comonomerer.To obtain the high clarity required for contact lens applications, it is particularly useful to use comonomers or comonomer mixtures whose corresponding polymers closely match solubility parameters (δ) and / or refractive index (RI) with the values for polydimethylsiloxane (6 = 15, RI = 1.43). Examples of such monomers are isobornyl methacrylate, tert-butyl methacrylate and mixtures of hydrocarbon methacrylates (RI 1.46) with fluorine-containing monomers such as hexafluoroisopropyl methacrylate, trifluoroethyl methacrylate, 1,1,2,2-tetrahydroperfluroalkurate perfluoroalkyl hexyl methacrylate, wherein alkyl is a carbon chain of 5-12 carbon atoms (RI values of 1.38-1.40) (δ <15). Furthermore, perfluoroalkyl group-containing monomers greatly enhance the oxygen permeability of polymers in a synergistic manner with the polysiloxane. They are therefore the particularly preferred comonomers.

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1212

Til fremstilling af hårde linser er det foretrukne monomerindhold 50-85 vægtprocent, beregnet på den totale polymer, idet den foretrukne comonomer er methylmethacrylat, cyclo-hexylmethacrylat, isobornylmethacrylat, isopropylmethacrylat, 5 isobutylmethacrylat, tert.butylmethacrylat eller hexafluor-isopropylmethacrylat eller blandinger deraf.For the preparation of hard lenses, the preferred monomer content is 50-85% by weight based on the total polymer, the preferred comonomer being methyl methacrylate, cyclohexylmethacrylate, isobornylmethacrylate, isopropylmethacrylate, isobutylmethacrylate, tert.butylmethacrylate or tert.butylmethacrylate.

Mest foretrukket er comonomeren methylmethacrylat, isobornylmethacrylat, isopropylmethacrylat, isobutylmethacrylat eller cyclohexylmethacrylat eller blandinger deraf. Mest foretrukket 10 er ligeledes blandinger af methylmethacrylat og/eller isobornylmethacrylat med 1 - 25 vægtprocent, beregnet på den totale monomer, af et kortkædet tværbindingsmiddel neopen-tylenglycoldiacrylat, ethylenglycoldimethacrylat eller reaktionsproduktet af 1 mol isophorondiisocyanat og 2 mol 15 2-hydroxyethylmethacrylat.Most preferably, the comonomer is methyl methacrylate, isobornyl methacrylate, isopropyl methacrylate, isobutyl methacrylate or cyclohexyl methacrylate or mixtures thereof. Most preferred are also mixtures of methyl methacrylate and / or isobornyl methacrylate with 1 to 25% by weight, based on the total monomer, of a short chain cross-linking agent neopethylene glycol diacrylate, ethylene glycol dimethacrylate or the reaction product of 1 mol of isophorone diacyanate and 2

Et andet stærkt foretrukket comonomersystem til fremstilling af hårde linser er vinylacetat/dimethvlmaleat (i molforhold fra 2/1 til 5/1) plus en foretrukket methacrylatmonomer ifølge ovenstående opregning.Another highly preferred comonomer system for the preparation of hard lenses is vinyl acetate / dimethyl maleate (in molar ratios from 2/1 to 5/1) plus a preferred methacrylate monomer as listed above.

20 Til fremstilling af bløde linser er den foretrukne comonomer 2-ethylhexylacrylat, 2-ethvlhexylmethacrylat, n-butylacrylat, n-butylmethacrylat, n-octylacrylat, n-octylmethacrylat, n-decylacrylat, n-decylmethacrylat, perfluoralkyl-(Cg_^Q)-substitueret alkylacrylat eller methacrylat eller blandin-25 ger deraf.For the preparation of soft lenses, the preferred comonomer is 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, n-butyl acrylate, n-butyl methacrylate, n-octyl acrylate, n-octyl methacrylate, n-decyl acrylate, n-decyl methacrylate, n-decyl methacrylate. substituted alkyl acrylate or methacrylate or mixtures thereof.

De kontaktlinser, der er fremstillet ud fra de her omhandlede polymerer, er fri for fyldstof, hydrolytisk stabile, biologisk indifferente, transparente og tilstrækkeligt permeable for oxygen til at tillade en tilstrækkelig oxygentilførsel 30 til at opfylde den menneskelige hornhindes krav.The contact lenses made from the polymers herein are free of filler, hydrolytically stable, biologically inert, transparent and sufficiently permeable to oxygen to allow a sufficient oxygen supply 30 to meet the requirements of the human cornea.

Den vandopløselige vinylmonomer (B2), der kan anvendes ved 13The water-soluble vinyl monomer (B2) that can be used at 13

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den foreliggende opfindelse, er fortrinsvis acrylater og methacrylater med den almene strukturThe present invention is preferably acrylates and methacrylates of the general structure

RR

H2C=i=COOR13 hvor R13 betyder en carbonhydrid gruppe med 1-10 carbonatomer, 5 der er substitueret med en eller flere vandopløseliggørende grupper, såsom carboxy-, hydroxy- eller tert.amino-grupper, eller en polyethylenoxidgruppe med 2-100 gentagne enheder eller en gruppe, der indeholder sulfat-, phosphat-, sulfonat-eller phosphonatgrupper; acrylamider og methacrylamider 10 med strukturen CHo=C-C00NHR1„ 2 | 14 R3 hvor har samme betydning som R^3 eller Rj.; acrylamider og methacrylamider med strukturenH 2 C = i = COOR 13 where R 13 means a hydrocarbon group having 1-10 carbon atoms substituted by one or more water-solubilizing groups such as carboxy, hydroxy or tert-amino groups, or a polyethylene oxide group having 2-100 repeating units or a group containing sulfate, phosphate, sulfonate or phosphonate groups; acrylamides and methacrylamides 10 having the structure CHo = C-C00NHR1 "2 | R3 where has the same meaning as R3 or R3; acrylamides and methacrylamides of structure

/RS/ RS

HoC=C-C0Nf I \ R3 Xr5 15 maleater og fumarater med strukturen HCOOR1 -j II 13 HCOOR13 vinylethere med strukturen h2c=ch-or13 og N-vinyllactamer, såsom N-vinyl-2-pyrrolidon.HoC = C-CONf I \ R3 Xr5 maleate and fumarates of structure HCOOR1 -j II 13 HCOOR13 vinyl ethers of structure h2c = ch-or13 and N-vinyl lactams such as N-vinyl-2-pyrrolidone.

20 De anvendelige, vandopløselige monomerer omfatter bl.a.The useful water-soluble monomers include, inter alia,

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14 2-hydroxyethyl-, 2- og 3-hydroxypropyl-, 2,3-dihydroxypropyl-, polyethoxyethyl- og polyethoxypropylacrylater og -methacry-later samt de tilsvarende acrylamider og methacrylamider, saccharose-, mannose-, glucose-, sorbitolacrylater og -meth-5 aerylater; acrylamid og methacrylamid> N-methylacryl og -methacrylamid, bisacetoneacrylamid, 2-hydroxyethylacryl-amid, dimethylacrylamid og -methacrylamid, methylolacryl-amid og -methacrylamid; Ν,Ν-dimethyl- og N,N-diethylamino-ethylacrylat og -methacrylat samt de tilsvarende acrylamider 10 og methacrylamider, N-tert.butylaminoethylmethacrylat og -methacrylamid, 2- og 4-vinylpyridin, 4- og 2-methyl-5-vinyl-pyridin, N-methyl-4-vinylpiperidin, 1-vinyl- og 2-methyl--1-vinylimidazol, dimethylallylamin og methyldiallylamin, para- og ortho-aminostyren, dimethylaminoethylvinylether, 15 N-vinylpyrrolidon, 2-pyrrolidinoethylmethacrylat; acryl- og methacrylsyre, itacon-, kanel-, croton-, fumar- og malein-syre samt lavere hydroxyalkylmono- og -diestere deraf, såsom 2-hydroxyethyl- og di-(2-hydroxy)-ethylfumarat, -maleåt og -itaconat samt 3-hydroxypropylbutylfumarat og di-polyalkoxy-20 alkylfumarater, -maleater og -itaconater; maleinsyreanhydrid, natriumacrylat og -methacrylat, 2-methacryloyloxyethyl-sulfonsyre, 2-acrylamido-2-methylpropansulfonsyre, 2-phos-phatoethylmethacrylat, vinylsulfonsyre, natriumvinylsulfonat, p-styrensulfonsyre, natrium-p-styrensulfonat og allylsulfon-25 syre.14 2-hydroxyethyl, 2- and 3-hydroxypropyl, 2,3-dihydroxypropyl, polyethoxyethyl and polyethoxypropyl acrylates and methacrylates and the corresponding acrylamides and methacrylamides, sucrose, mannose, glucose, sorbitol acrylates and meth. -5 aerylates; acrylamide and methacrylamide> N-methylacrylamide and methacrylamide, bisacetone acrylamide, 2-hydroxyethylacrylamide, dimethylacrylamide and methacrylamide, methylolacrylamide and methacrylamide; Ν, Ν-dimethyl and N, N-diethylamino-ethyl acrylate and methacrylate, and the corresponding acrylamides 10 and methacrylamides, N-tert-butylaminoethyl methacrylate and methacrylamide, 2- and 4-vinylpyridine, 4- and 2-methyl-5- vinyl pyridine, N-methyl-4-vinylpiperidine, 1-vinyl and 2-methyl-1-vinylimidazole, dimethylallylamine and methyldiallylamine, para- and ortho-amino styrene, dimethylaminoethylvinyl ether, N-vinylpyrrolidone, 2-pyrrolidinoethyl methacrylate; acrylic and methacrylic acid, itaconic, cinnamon, crotonic, fumaric and maleic acids and lower hydroxyalkyl mono and diesters thereof, such as 2-hydroxyethyl and di- (2-hydroxy) ethyl fumarate, maleate and itaconate and 3-hydroxypropylbutyl fumarate and di-polyalkoxyalkyl fumarates, maleate and itaconates; maleic anhydride, sodium acrylate and methacrylate, 2-methacryloyloxyethyl sulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, 2-phosphatoethyl methacrylate, vinyl sulfonic acid, sodium vinyl sulfonate, p-styrene sulfonic acid, sodium p-styrene sulfate and sodium p-styrene sulfate

Anvendelige er ligeledes de kvaterniserede derivater af kationiske monomerer, der er fremkommet ved kvaterniserihg med udvalgte alkyleringsmidler, såsom halogenerede carbon-hydrider, f.eks. methyliodid, benzylchlorid eller hexadecyl-30 chlorid, epoxider, såsom glycidol, epichlorhydrin og eth- ylenoxid, acrylsyre, dimethylsulfat, methvlsulfat og propan-sulton.Also useful are the quaternized derivatives of cationic monomers obtained by quaternization with selected alkylating agents such as halogenated hydrocarbons, e.g. methyl iodide, benzyl chloride or hexadecyl chloride, epoxides such as glycidol, epichlorohydrin and ethylene oxide, acrylic acid, dimethyl sulfate, methyl sulfate and propane sultone.

En mere komplet liste over vandopløselige monomerer, der er anvendelige ved den her omhandlede opfindelse, er.angivet i 15A more complete list of water-soluble monomers useful in the present invention is set forth in FIG.

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R.H. Yocum, E.B. Nyquist, Functional Monomers, bind 1, side 424-440 (M. Dekker, N.Y. 1973).R.H. Yocum, E.B. Nyquist, Functional Monomers, Volume 1, pages 424-440 (M. Dekker, N.Y. 1973).

Foretrukne monomerer er: (B^) = methylmethacrylat, cyclohexylmethacrylat, isobornyl-5 methacrylat, t-butyl- og isobutylmethacrylat, isopropyl-methacrylat og hexafluorisopropylmethacrylat.Preferred monomers are: (B 1) = methyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, t-butyl and isobutyl methacrylate, isopropyl methacrylate and hexafluoro isopropyl methacrylate.

(B2) = 2-hydroxyethylmethacrylat, Ν,Ν-dimethylacrylamid, acryl- og methacrylsyre og N-vinyl-2-pyrrolidon.(B2) = 2-hydroxyethyl methacrylate, Ν, Ν-dimethylacrylamide, acrylic and methacrylic acid and N-vinyl-2-pyrrolidone.

Foruden monovinylforbindelserne kan der anvendes en bred mang-10 foldighed af divinylforbindelser. Fra 1 til 25% af vægten af den totale monomer B kan faktisk være en diolefinisk monomer (B ). Eksempler på diolefiniske monomerer er allylacrylat og -methacrylat, ethylenglycol-, diethylenglycol-, trieth-ylenglycol-, tetraethylenglycol- og generelt polyethylen-15 oxidglycoldiacrylater og -dimethacrylater, 1,4-butandiol-og poly-n-butylenoxidglycoldiacrylater og -dimethacrylater, propylenglycol- og polypropylenoxidglycoldiacrylater og -dimethacrylater, thiodiethylenglycoldiacrylat og -dimethacrylat, di-(2-hydroxyethyl)-sulfondiacrylat og -dimethacrylat, neo-20 pentylenglycoldiacrylat og -dimethacrylat, trimethylolpropan- tri- og -tetraacrylat, pentaerythritoltri- og -tetraacrylat, divinylbenzen, divinylether, divinylsulfon, disiloxanyl--bis-3-hydroxypropyldiacrylat eller -methacrylat og beslægtede forbindelser; bisphenol A-diacrylat eller -dimeth-25 acrylat, ethoxyleret bisphenol A-diacrylat eller -dimeth- acrylat, methylenbisacrylamid eller -methacrylamid, dimeth-ylenbisacrylamid eller -methacrylamid, Ν,Ν'-dihydroxyethylen-bisacrylamid eller -methacrylamid, hexamethylenbisacrylamid eller -methacrylamid, decamethylenbisacrylamid eller -meth-30 acrylamid, allyl- og diallylmaleat, triallylmelamin, diallyl-itaconat, diallylphthalat, triallylphosphit, polyallylsac-charose, saccharosediacrylat og glucosedimethacrylat; ligeledes umættede polyestere, såsom poly-(alkylenglycolmaleater) og poly-(alkylenglycolfumarater), såsom poly-(propylenglycol-In addition to the monovinyl compounds, a wide variety of divinyl compounds can be used. Indeed, from 1 to 25% of the weight of the total monomer B may be a diolefinic monomer (B). Examples of diolefinic monomers are allyl acrylate and methacrylate, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol and generally polyethylene oxide glycol diacrylates and dimethacrylates, 1,4-butanediol dimethylacetylacetate - and polypropylene oxide glycol diacrylates and dimethacrylates, thiodiethylene glycol diacrylate and dimethacrylate, di- (2-hydroxyethyl) sulfone diacrylate and dimethacrylate, neo-pentylene glycol diacrylate and dimethacrylate and trimethylacrylate, trimethylol triacrylate divinylsulfone, disiloxanyl - bis-3-hydroxypropyl diacrylate or methacrylate and related compounds; bisphenol A diacrylate or dimethacrylate, ethoxylated bisphenol A diacrylate or dimethacrylate, methylene bisacrylamide or methacrylamide, dimethylene bisacrylamide or methacrylamide, Ν, Ν'-dihydroxyethylene , decamethylene bisacrylamide or methacrylamide, allyl and diallyl maleate, triallyl melamine, diallyl itaconate, diallyl phthalate, triallyl phosphite, polyallylsaccharose, sucrose diacrylate and glucose dimethacrylate; also unsaturated polyesters such as poly (alkylene glycol maleate) and poly (alkylene glycol fumarates) such as poly (propylene glycol)

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16 maleat) og poly-(polyalkylenoxidglycolmaleat).16 maleate) and poly (polyalkylene oxide glycol maleate).

Som tværbindingsmidler kan der ligeledes anvendes de reaktionsprodukter, der er fremkommet ved omsætning af 1 mol dieller tri-isocyanat med strukturen OCN-R^-(NCO)^ ener 2' 5 hvor har den ovenfor angivne betydning, med 2 eller 3 mol af et hydroxyalkylacrylat eller -methacrylat eller en hydroxy-alkylvinylether eller allylalkohol eller N-tert.butylamino-ethylmethacrylat eller bis-hydroxyethylmaleat eller en hvilken som helst af de aktivt hvdrogen-holdige forbindelser, 10 der er anført ovenfor.Also used as cross-linking agents are the reaction products obtained by reacting 1 mole of tri-isocyanate with the structure OCN-R 2 - (NCO) 2 and 5 having the meaning given above, with 2 or 3 moles of a hydroxyalkyl acrylate or methacrylate or a hydroxyalkyl vinyl ether or allyl alcohol or N-tert-butylaminoethyl methacrylate or bis-hydroxyethyl maleate or any of the active hydrogen-containing compounds listed above.

Den diolefiniske monomer (B ) er fortrinsvis acrylatet eller Λ methacrylatet af allylalkohol, af en ligekædet eller forgrenet alkylenglycol med 2-6 carbonatomer, af poly-(ethylen-« oxid)-glycol, af poly-(propylenoxid)-glycol, af poly-(n-but-15 ylenoxid)-glycol, af thiodiethylenglycol, af neopentylen- glycol, af trimethylolpropan eller af pentaerythritol, eller det reaktionsprodukt, der er fremkommet ved omsætning af 1 mol di- eller triisocyanat med strukturen OCN-R^-(NCO)v, hvor R4 har den ovenfor angivne betydning, og v er 1 eller 2, 20 med 2 eller 3 mol af et hydroxyalkylacrylat eller -methacrylat .The diolefinic monomer (B) is preferably the acrylate or Λ methacrylate of allyl alcohol, of a straight or branched alkylene glycol of 2-6 carbon atoms, of poly (ethylene oxide) glycol, of poly (propylene oxide) glycol, of poly - (n-butylene oxide) glycol, of thiodiethylene glycol, of neopentylene glycol, of trimethylolpropane or of pentaerythritol, or of the reaction product obtained by reaction of 1 mole of di- or triisocyanate with the structure OCN-R NCO) v, wherein R4 is as defined above and v is 1 or 2, 20 with 2 or 3 moles of a hydroxyalkyl acrylate or methacrylate.

En ylerst foretrukket difunktionel comonomer (Βχ) er 1 - 251, beregnet på vægten af den totale monomer, neopentylenglycol-diacrylat, reaktionsproduktet af 1 mol isophorondiisocyanat 25 og 2 mol 2-hydroxyethylmethacrylat eller ethylenglycoldi-methacrylat.A most preferred difunctional comonomer (Βχ) is 1 - 251, based on the weight of the total monomer, neopentylene glycol diacrylate, the reaction product of 1 mole of isophorone diisocyanate 25 and 2 moles of 2-hydroxyethyl methacrylate or ethylene glycol dimethacrylate.

Monomererne kan anvendes alene eller i kombination med hinanden, idet der skal drages den nødvendige omsorg for deres polymerisationsparametre for at sikre, at der sker en tilfæl-30 dig copolymerisation. Hvis polymererne skal anvendes til kontaktlinser, er en høj klarhedsgrad og farveløshed endvidere essentiel for udvælgelsen af en hensigtsmæssig monomerkombination.The monomers can be used alone or in combination with each other, due care being taken to their polymerization parameters to ensure that random copolymerization occurs. Furthermore, if the polymers are to be used for contact lenses, a high degree of clarity and colorlessness is essential for the selection of an appropriate monomer combination.

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1717

En foretrukken udførelsesform for den foreliggende opfindelse er en polymer, hvor komponent A er en polysiloxan med strukturen ki eller A2, Ri betyder alkylen med 3 eller 4 car-bonatomer, X betyder -Z^CONH-R^NHCO-, hvor Ζχ betyder -0-5 eller -NH-, og R4 betyder et diradikal af et aliphatisk eller cycloaliphatisk diisocyanat med 6-10 carbonatomer, og Y betyder -Z2-R8-Z2-CO-C=CHA preferred embodiment of the present invention is a polymer in which component A is a polysiloxane of structure k 1 or A 2, R 1 is alkylene of 3 or 4 carbon atoms, X is -Z 2 CONH-R 2 NHCO-, where Ζχ means - 0-5 or -NH-, and R4 represents a diradical of an aliphatic or cycloaliphatic diisocyanate of 6-10 carbon atoms, and Y means -Z2-R8-Z2-CO-C = CH

R3 r6 10 hvor R6 betyder hydrogen, R8 betyder ethylen, og Z2 betyder -O- eller -NC(CH3)3~, og komponent B indeholder fra 1 til 25%, beregnet på den totale monomer, af en diolefinisk monomer (Bx), der er acrylatet eller methacrylatet af allylalko-hol, af en ligekædet eller forgrenet alkylenglycol med 2-6 15 carbonatomer, af poly-(ethylenoxid)-glycol, af poly-(propyl-enoxid)-glycol, af poly-(n-butylenoxid)-glycol, af thiodi-ethylenglycol, af neopentylenglycol, af trimethylolpropan eller af pentaerythritol, eller reaktionsproduktet dannet ved omsætning af 1 mol di- eller tri-isocyanat med strukturen 20 0CN-R4-(NC0)v, hvor R4 har den ovenfor angivne betydning, og v er 1 eller 2, med 2 eller 3 mol hydroxyalkylacrylat eller -methacrylat.R3 is R6 where R6 is hydrogen, R8 is ethylene, and Z2 is -O- or -NC (CH3) 3 ~, and component B contains from 1 to 25%, based on the total monomer, of a diolefinic monomer (Bx) , which is the acrylate or methacrylate of allyl alcohol, of a straight or branched alkylene glycol of 2-6 carbon atoms, of poly (ethylene oxide) glycol, of poly (propylene oxide) glycol, of poly (n butylene oxide) glycol, of thiodiethylene glycol, of neopentylene glycol, of trimethylolpropane or of pentaerythritol, or the reaction product formed by reaction of 1 mole of di- or tri-isocyanate having the structure 20CN-R4- (NC0) v, where R4 has the above and v is 1 or 2, with 2 or 3 moles of hydroxyalkyl acrylate or methacrylate.

Polyfunktionelle polysiloxaner, der kan anvendes som udgangs-25 materialer til makromeren (A), har formlen . p η 30 HZ1R1--SiO---jiO--SiO---ji-RiZiH (I) 2 xi Ϊ1 f e I h Xz L i.H Jyi 1 ellerPolyfunctional polysiloxanes which can be used as starting materials for the macromer (A) have the formula. p η 30 HZ1R1 - SiO --- jiO - SiO --- ji-RiZiH (I) 2 xi Ϊ1 f e I h Xz L i.H Jyi 1 or

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18 5 (R2)3Si0--jiO---jiO--jiO---Si(R2)3 (II) ' ' li ^ ” Jy2 + 1 10 hvor R^, R2, ^b/ ^d' ^f/ Rg/ ^h* ^if ^j · ^k'18 5 (R2) 3 SiO - jiO --- jiO - jiO --- Si (R2) 3 (II) '' li ^ ”Jy2 + 1 10 where R ^, R2, ^ b / ^ d '^ f / Rg / ^ h * ^ if ^ j · ^ k '

Zlf x^, X2, Yi og Y2 har de ovenfor angivne betydninger.Zlf x 2, X 2, Y 1 and Y 2 have the above meanings.

Diisocyanater, der kan anvendes til fremstilling af præpoly-15 mer-mellemproduktet, er aliphatiske, cycloaliphatiske eller aromatiske isocyanater med formlenDiisocyanates which can be used to prepare the prepolymer intermediate are aliphatic, cycloaliphatic or aromatic isocyanates of the formula

OCN-R4-NCOOCN-R4-NCO

20 som omfatter ethylendiisocyanat, 1,2 -diisocyanatpropan, 1,3 -diisocyanatpropan, 1,6-diisocyanathexan, 1,2-diisocyanat-cyclohexan, 1,3-diisocyanatcyclohexan, 1,4-diisocyanatcyclo-hexan, o-diisocyanatbenzenf m-diisocyanatbenzen, p-diisocya-natbenzen, bis-(4-isocyanatcyclohexyl)-methan, bis-(4-iso-25 cyanatcyclohexanyl) -methan, bis- (4-isocyanatphenyl) -methan, toluendiisocyanat, 3, 3-dichlor-4,4'-diisocyanatbiphenyl, 1,5-diisocyanatnaphthalen, hydrogeneret toluendiisocyanat, l-isocyanatmethyl-5-isocyanat-l,3,3-trimethylcyclohexan (=isophorondiisocyanat), 1,6-diisocyanat-2,2,4-(2,4,4)-tris-3 0 methylhexan, 2,2' -di isocyanatdiethyl fumarat, 1,5-diisocyanat- 1-carboxypentan, 1,2-, 1,3-, 1,5-, 1,6-, 1,7-, 1,8-, 2,7-og 2,3-diisocyanatnaphthalen, 2,4- og 2,7-diisocyanat-l-methylnaphthalen, 1,4-diisocyanat-methylcyclohexan, 1,3-diisocyanat-6 (7) -methylnaphthalen, 4,4'-diisocyanatbiphenyl, 35 4,4' -diisocyanat-3,3 ' -dimethoxy-bisphenyl, 3,3'- og 4,4'- diisocyanat-2,21 -dimethylbiphenyl, bis- (4-isocyanatphenyl) -Which includes ethylene diisocyanate, 1,2-diisocyanate propane, 1,3-diisocyanate propane, 1,6-diisocyanate hexane, 1,2-diisocyanate-cyclohexane, 1,3-diisocyanate cyclohexane, 1,4-diisocyanate cyclohexane, o-diisocyanate benzene diisocyanate benzene, p-diisocyanate benzene, bis (4-isocyanate cyclohexyl) methane, bis- (4-isocyanate cyclohexanyl) methane, bis- (4-isocyanate phenyl) methane, toluene diisocyanate, 3,3-dichloro , 4'-diisocyanate biphenyl, 1,5-diisocyanate naphthalene, hydrogenated toluene diisocyanate, 1-isocyanate methyl-5-isocyanate-1,3,3-trimethylcyclohexane (= isophorone diisocyanate), 1,6-diisocyanate-2,2,4- (2, 4,4) -tris-methylhexane, 2,2'-diisocyanate diethyl fumarate, 1,5-diisocyanate-1-carboxypentane, 1,2-, 1,3-, 1,5-, 1,6-, 1,7-, 1,8-, 2,7- and 2,3-diisocyanate naphthalene, 2,4- and 2,7-diisocyanate-1-methylnaphthalene, 1,4-diisocyanate methylcyclohexane, 1,3-diisocyanate 6 (7) -methylnaphthalene, 4,4'-diisocyanate biphenyl, 4,4'-diisocyanate-3,3 '-dimethoxy-bisphenyl, 3,3'- and 4,4'-diisocyanate-2,21-dimethylbiphenyl,bis- (4-isocyanate phenyl) -

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19 ethan og bis-(4-isocyanatphenyl)-ether.19 ethane and bis (4-isocyanate phenyl) ether.

Diisocyanaterne kan anvendes alene eller i kombination med hinanden.The diisocyanates can be used alone or in combination with each other.

55

Aktivt-hydrogenholdige monomerer, der kan anvendes til at maskere polysiloxanpolyisocyanatet i endestilling, omfatter forbindelser med formlenActive-hydrogen-containing monomers which can be used to mask the polysiloxane polyisocyanate at the end position include compounds of the formula

10 H-Z2-R8"Z2-C-C=CHH-Z2-R8 "Z2-C-C = CH

II I III I I

O R3 Rg hvor R3, R6, Rg og Z2 har den ovenfor angivne betydning, og 15 som således er aktivt-hydrogenholdige acrylater, methacry-later, fumarater, maleater og de tilsvarende amider, såsom 2-hydroxyethyl-, 2 og 3-hydroxypropyl-, 2,3-dihydroxyprop-yl-, polyethoxy-, polyethoxypropyl-, polypropoxy-propylacry-later og -methacrylater samt de tilsvarende acrylyl- og 20 methacrylamider, 2-hydroxyethyl- og bis-(2-hydroxyethyl)-fumarat, hydroxypropylbutylfumarat, N-(2-hydroxyethyl)-male-imid og N-(2-hydroxyethoxyethyl)-maleimid, tert-butylamino-ethylmethacrylat, pentaerythritolmono-, -diacrylat.O R3 Rg wherein R3, R6, Rg and Z2 are as defined above and thus are active-hydrogen-containing acrylates, methacrylates, fumarates, maleate and the corresponding amides such as 2-hydroxyethyl, 2 and 3-hydroxypropyl -, 2,3-dihydroxypropyl, polyethoxy, polyethoxypropyl, polypropoxy propylacrylates and methacrylates, and the corresponding acrylyl and methacrylamides, 2-hydroxyethyl and bis (2-hydroxyethyl) fumarate, hydroxypropylbutyl fumarate , N- (2-hydroxyethyl) -maleimide and N- (2-hydroxyethoxyethyl) -maleimide, tert-butylamino-ethyl methacrylate, pentaerythritol mono-, diacrylate.

25 Andre anvendelige forbindelsesklasser er allylmonomerer, såsom allylalkohol og methallylalkohol samt diallylamin, og vinylethere med formlen H2c=CH-0-Rj-0H, hvor R7 har den ovenfor angivne betydning, f.eks. 4-hydroxybutylvinylether. 1Other useful classes of compounds are allyl monomers such as allyl alcohol and methallyl alcohol as well as diallylamine, and vinyl ethers of the formula H2c = CH-O-Rj-OH, where R7 has the meaning given above, e.g. 4-hydroxybutyl vinyl ether. 1

En liste over monomerer, som kan anvendes ved den foreliggende opfindelse, findes i R.H. Yocum, E.B. Nyquist; Functional Monomers, bind 1, side 424-440 (M. Dekker, N.Y. 1973).A list of monomers which can be used in the present invention can be found in R.H. Yocum, E.B. Nyquist; Functional Monomers, Volume 1, pages 424-440 (M. Dekker, N.Y. 1973).

OISLAND

2020

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Polysiloxan-polyisocyanatpræpolymeren kan også være maskeret med umættede syrer under anvendelse af en basisk katalysator eller en metalkatalysator, hvilket resulterer i en amidbinding med udvikling af C02· Anvendelige syrer omfatter acryl-5 syre, methacrylsyre, fumarsyre, maleinsyre, itaconsyre og kanelsyre.The polysiloxane-polyisocyanate prepolymer may also be masked with unsaturated acids using a basic catalyst or a metal catalyst, resulting in an amide bond with the development of CO 2. Useful acids include acrylic acid, methacrylic acid, fumaric acid, maleic acid, itaconic acid.

Monomererne og , diisocyanaterne og de polyfunktionelle polysiloxanudgangsmaterialer til A er stort set haidelsprodukter.The monomers and, the diisocyanates and the polyfunctional polysiloxane starting materials for A are largely skin products.

1010

Polysiloxanmakromererne fremstilles bekvemt ved en totrinssyntese ud fra de tilsvarende polyfunktionelle polysiloxaner.The polysiloxane macromers are conveniently prepared by a two-step synthesis from the corresponding polyfunctional polysiloxanes.

I det mest foretrukne tilfælde er disse dioler eller poly-oler, men de kan også være amino-funktionelle eller mercapto-15 -funktionelle polysiloxaner. Som første trin omsættes poly-siloxanen, enten som masse eller i opløsning, med en givet mængde af et di- eller triisocyanat i nærværelse af en vilkårlig af de konventionelle katalysatorer. Disse katalysatorer kan være forbindelser indeholdende tertiære aminogrup-20 per, såsom triethylamin, pyridin eller diaminobicyclooctan, eller metalbaserede katalysatorer, såsom dibutyltindilaurat eller stannooctoat. Reaktionen gennemføres ved enten stuetemperatur eller forhøjet temperatur under en kappe af tørt nitrogen og kan bekvemt efterfølges af NCO-titrering eller 25 IR-analyse. Ved anvendelse af diisocyanat falder procenten af NCO til en beregnet procent af den oprindelige værdi, og reaktionsproduktet fra første trin består af et polysiloxan-diisocyanat. Molforholdet mellem OH- og NCO-grupper i første reaktionstrin kan være 1:1,5 - 1:3, og det ligger for-30 trinsvis i området 1:2,05 - 1:2,1.In the most preferred case, these are diols or polyols, but they may also be amino-functional or mercapto-15-functional polysiloxanes. As the first step, the poly-siloxane, either as a mass or in solution, is reacted with a given amount of a di- or triisocyanate in the presence of any of the conventional catalysts. These catalysts may be compounds containing tertiary amino groups such as triethylamine, pyridine or diaminobicyclooctane, or metal-based catalysts such as dibutyltin dilaurate or stannous octoate. The reaction is carried out at either room temperature or elevated temperature under a dry nitrogen jacket and can be conveniently followed by NCO titration or IR analysis. When using diisocyanate, the percentage of NCO drops to a calculated percentage of the original value and the reaction product from the first step consists of a polysiloxane diisocyanate. The molar ratio of OH and NCO groups in the first reaction step can be 1: 1.5 - 1: 3, and it is preferably in the range of 1: 2.05 - 1: 2.1.

Omsætningens andet trin består af en maskering af polyiso-cyanatet i endestilling med en hydroxy- eller amino-funktionel vinylforbindelse, mest almindeligt med 2-hydroxyethylmeth-35 acrylat. Det er tilrådeligt at anvende mindst et ringe overskud af den monomer, der anvendes til maskeringen i endestilling, typisk et molforhold af OH, SH og NR til NCO på 1,05:1 eller derover. Eftersom det er foretrukket prak- 21The second step of the reaction consists of an end position masking of the polyisocyanate with a hydroxy or amino-functional vinyl compound, most commonly with 2-hydroxyethyl methacrylate. It is advisable to use at least a slight excess of the monomer used for the end position masking, typically a molar ratio of OH, SH and NR to NCO of 1.05: 1 or greater. Since it is preferred practice

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OISLAND

sis at inkorporere en ringe mængde af en vandopløselig monomer i slutpolymeren for at opnå gode befugtningskarakteri-stika, er et større overskud af den hydroxy- eller amino-funk-tionelle monomer ikke skadelig. Reaktionen forløber ved stue-5 temperatur eller forhøjet temperatur over en periode på adskillige timer uden behov for yderligere katalysator. Da der normalt ikke er inhibitorer til stede, er en oxygenfri nitrogenatmosfære essentiel. Reaktionens afslutning bestemmes let ved IR-spektroskopi ved konstatering af fravær af -NCD-grupper.For example, when incorporating a small amount of a water-soluble monomer into the final polymer to obtain good wetting characteristics, a greater excess of the hydroxy or amino-functional monomer is not detrimental. The reaction proceeds at room temperature or elevated temperature over a period of several hours without the need for additional catalyst. Since no inhibitors are normally present, an oxygen-free nitrogen atmosphere is essential. The termination of the reaction is readily determined by IR spectroscopy in the absence of -NCD groups.

1010

Undertiden er det praktisk, f.eks. ved anvendelse af meget højviskose materialer, at gennemføre makromersyntesens andet trin i en monomeropløsning, der svarer til det ønskede slut-polymermateriale.Sometimes it is convenient, e.g. using very high viscous materials, to perform the second step of macromers synthesis in a monomer solution corresponding to the desired final polymer material.

1515

Selv om det foretrækkes at omsætte 1 ækvivalent reaktiv poly-siloxan med tæt ved to ækvivalenter diisocyanat og derved opnå en i endestilling med isocyanat maskeret polysiloxan, kan der ifølge polykondensationskinetikkens love opnås en 20 vis mængde kædeforlænget produkt, hvor den i endestilling maskerede polymer indeholder to polysiloxankæder, der er forbundet via en diisocyanatenhed, og dette kædeforlængede produkt kan analyseres, f.eks. ved gelpermeationschromatografi. 1 2 3 4 5 6 7 8 9 10 11 ved den foreliggende opfindelse kan der som 2 polysiloxaner også anvendes præpolymerer, der er fremstil 3 let ud fra polysiloxaner med strukturen I og II ved kæde 4 forlængelsesreaktioner, der er almindeligt anvendte af fag- 5 mænd inden for polykondensationsteknikken, især polyurethan- 6 kemien. Sådanne kædeforlængelser kan f.eks. opnås ved poly- 7 kondensation af ovennævnte polysiloxandioler, -dithioler el 8 ler -diaminer med disyrechlorider eller svredianhydrider 9 eller disyredianhydrider, såsom terephthaloylchlorid, adipin- 10 syredichlorid, maleinsyreanhydrid, phthalsyreanhydrid eller 11 benzophenon-tetracarboxylsvre og -dianhydrid, med diisocya-nater med ovennævnte strukturer, i hvilket tilfælde syntesetrinet til fremstilling af den NCO-maskerede makromerAlthough it is preferable to react 1 equivalent of reactive polysiloxane with close to two equivalents of diisocyanate, thereby obtaining a polysiloxane-masked terminus, according to the laws of polycondensation kinetics, a certain amount of chain-extended polymer may be obtained where the terminally-coated polymer contains polysiloxane chains linked via a diisocyanate moiety and this chain elongated product can be analyzed, e.g. by gel permeation chromatography. 1 2 3 4 5 6 7 8 9 10 11 In the present invention, as 2 polysiloxanes, prepolymers prepared 3 readily from polysiloxanes of structure I and II at chain 4 extension reactions commonly used in the art can also be used. men in the polycondensation technique, especially polyurethane chemistry. Such chain extensions may e.g. is obtained by poly-condensation of the above-mentioned polysiloxane diols, dithiols or 8-diamines with diacetic chlorides or sulfuric anhydrides 9 or diacid dianhydrides such as terephthaloyl chloride, adipic acid dichloride, maleic anhydride, tetraic anhydride and phthalic anhydride or 11 the above structures, in which case the synthesis step of producing the NCO masked macromer

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22 som beskrevet ovenfor simpelt hen gennemføres med under et 2:1-overskud af NCO i forhold til -OH-, -SH- eller -NI^--grupper. På samme måde kan de NCO-afsluttede præpolymerer, 5 der er fremkommet, før det endelige maskeringstrin gennemføres med hydroxy-vinylforbindelserne, kædeforlænges med dioler eller diaminer ifølge den kendte teknik inden for polyurethanteknologien, f.eks. med ethylenglycol, propylen-glycol, butandiol, hexandiol, polyetherdioler indeholdende 10 ethylenoxid-, propylenoxid- eller n-butylenoxid-gentagne enheder, polyesterdioler, ethylendiamin, hexandiamin og diprimære eller disekundære aminer i almindelighed, herunder diaminer, der stammer fra polyalkylenoxider. I det omfang, der ved disse kædeforlængelsesreaktioner indføres yderligere 15 amid-, urethan- eller urinstofgrupper i strukturen, bidrager disse grupper til stivheden og klarheden af polymeren på grund af hydrogenbinding. Kædeforlængelser af den ovenfor beskrevne type fortynder imidlertid det samlede polysiloxan-indhold i præpolymeren, og der kræves følgelig en større 20 mængde af en sådan præpolymer for at bevare en høj oxygen-permeabilitet hos s lutpolymer en.22 as described above is simply carried out with less than a 2: 1 excess of NCO relative to -OH-, -SH- or -NII groups. Similarly, the NCO-terminated prepolymers obtained before the final masking step is carried out with the hydroxy-vinyl compounds can be chain extended with diols or diamines of the prior art in the polyurethane technology, e.g. with ethylene glycol, propylene glycol, butanediol, hexanediol, polyether diols containing 10 ethylene oxide, propylene oxide or n-butylene oxide repeating units, polyester diols, ethylene diamine, hexanediamine and diprimary or disecondary amines in general, including diamines derived from polyalkylene oxides. To the extent that in these chain extension reactions, an additional 15 amide, urethane or urea groups are introduced into the structure, these groups contribute to the stiffness and clarity of the polymer due to hydrogen bonding. However, chain extensions of the type described above dilute the total polysiloxane content of the prepolymer and, consequently, a greater amount of such prepolymer is required to maintain a high oxygen permeability of the sut polymer one.

De transparente, hårde og oxygenpermeable polymerer ifølge opfindelsen fremstilles i et slutsyntesetrin ved fri-radikal-25 copolymerisation, enten i masse eller i nærværelse af små mængder opløsningsmiddel.The transparent, hard and oxygen-permeable polymers of the invention are produced in a final synthesis step by free radical copolymerization, either in bulk or in the presence of small amounts of solvent.

Fremgangsmåden ifølge opfindelsen til fremstilling af copo-lymeren er ejendommelig ved, at man omsætter polysiloxanfor-30 bindeiser med formlenThe process of the invention for the preparation of the copolymer is characterized by reacting polysiloxane compounds of the formula

Ta ih Tc Td HZiRi--SiO---SiO--SiO---Si-Ri ZjH (I) ΙΛ JXl i» Af AeTa ih Tc Td HZiRi - SiO --- SiO - SiO --- Si-Ri ZjH (I) ΙΛ JXl i »By Ae

ZjH JxzZjH Jxz

Jyi /Jyi /

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23 eller fg Μ» fi (R2)3SiO--SiO---SiO--siO---Si(R2)3 (II)23 or fg Μ »fi (R2) 3 SiO - SiO --- SiO - siO --- Si (R2) 3 (II)

Jxj I *· J JX2 *yz + 1 hvori R]_, R2* R&* Rb* ^c< R^» R©» Rf» Rg» Rj\# Ri» Rj» Rk» 10 Z}, Xi, X2, yi og y2 har de ovenfor angivne betydninger, med diisocyanater med formlenJxj I * · J JX2 * yz + 1 wherein R] _, R2 * R & * Rb * ^ c <R ^ »R ©» Rf »Rg» Rj \ # Ri »Rj» Rk »10 Z}, Xi, X2 , y 1 and y 2 have the above meanings, with diisocyanates of the formula

OCN-R4-NCOOCN-R4-NCO

15 hvori R4 har den ovenfor angivne betydning, i nærværelse af en katalysator, maskerer de dannede polysiloxan-polyiso-cyanat-præpolymerer i endestilling ved omsætning med et lille overskud af aktiv hydrogen-holdige monomerer med formlen 20Wherein R 4 is as defined above, in the presence of a catalyst, the resulting polysiloxane-polyisocyanate prepolymers mask in the final position by reacting with a small excess of active hydrogen-containing monomers of formula 20

H-Z2-Ro-Z2-C-C=CHH-Z2-R-Z2-C-C = CH

2 8 2 11 i i o r3 r6 25 hvori R3, R6, Rg og Z2 har de ovenfor angivne betydninger, eller med allylalkohol eller methallylalkohol eller med forbindelser med formlen h2c=ch-o-r7-oh 30 hvori R7 har den ovenfor angivne betydning, til dannelse af polysiloxanmakromererne (A) , som man copolymeriserer med en vinylmonomer (B) valgt blandt en blanding af en vandopløselig monomer B2 og en vanduopløselig monomer B]_, en vand-35 uopløselig monomer B-l eller en blanding deraf, idet monomererne er monoolefiniske, en diolefinisk monomer Bx eller en blanding deraf, eller en blanding af monoolefiniske monomererWherein R3, R6, Rg and Z2 have the above meanings, or with allyl alcohol or methallyl alcohol or with compounds of the formula h2c = ch-o-r7-oh 30 wherein R7 has the meaning given above, to form the polysiloxane macromers (A) copolymerized with a vinyl monomer (B) selected from a mixture of a water-soluble monomer B2 and a water-insoluble monomer B], a water-insoluble monomer B1, or a mixture thereof, the monomers being monoolefinic , a diolefinic monomer Bx or a mixture thereof, or a mixture of monoolefinic monomers

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24 og diolefiniske monomerer, idet den monomere har den ovenfor angivne betydning, under anvendelse af en initiator, som danner frie radikaler.24 and diolefinic monomers, the monomer having the meaning given above, using an initiator which forms free radicals.

5 Polymerisationen gennemføres hensigtsmæssigt ved hjælp af varme, hensigtsmæssigt i nærværelse af en initiator, der udvikler frie radikaler, f.eks. ved en temperatur i området fa 40 til 105°C, idet de foretrukne temperaturområder ligger mellem 50 og 100*C. Disse initiatorer er fortrinsvis peroxi-10 der eller azo-katalysatorer med en halveringstid ved polymerisationstemperaturen på mindst 20 minutter. Typiske anvendelige peroxyforbindelser indbefatter isopropylpercarbonat, tert-butylperoctoat, benzoylperoxid, lauroylperoxid, decano-ylperoxid, acetylperoxid, ravsyreperoxid, methylethylketon-15 peroxid, tert-butylperoxyacetat, propionylperoxid, 2,4-di-chlorbenzoylperoxid, tert-butylperoxypivalat, pelargonyl-peroxid, 2,5-dimethyl-2,5-bis- (2-ethylhexanoylperoxy) -hexan, p-chlorbenzoylperoxid, tert-butylperoxybutyrat, tert-butyl-peroxymaleinsyre, tert-butylperoxyisopropylcarbonat og bis(l-20 hydroxycyclohexyl)-peroxid. Eksempler på azoforbindelser er 2,2-azo-bis-isobutyronitril, 2,2 '-azo-bis-(2,4-dimethyl-valeronitril), l,l'-azo-bis-(cyclohexancarbonitril) og 2,2’-azo-bis- (2,4-dimethyl-4-methoxyvaleronitril).The polymerization is conveniently carried out by heat, suitably in the presence of an initiator which develops free radicals, e.g. at a temperature in the range of 40 to 105 ° C, with the preferred temperature ranges being between 50 and 100 ° C. These initiators are preferably peroxides or azo catalysts with a half-life at the polymerization temperature of at least 20 minutes. Typical useful peroxy compounds include isopropyl percarbonate, tert-butyl peroctate, benzoyl peroxide, lauroyl peroxide, decanoyl peroxide, acetyl peroxide, succinic peroxide, methyl ethyl ketone peroxide, tert-butyl peroxyacetate, propionyl peroxide, propionyl peroxide, propionyl peroxide, propionyl peroxide, , 5-Dimethyl-2,5-bis (2-ethylhexanoylperoxy) hexane, p-chlorobenzoyl peroxide, tert-butyl peroxybutyrate, tert-butyl peroxymaleic acid, tert-butyl peroxyisopropyl carbonate and bis (1-hydroxycyclohexyl) peroxide. Examples of azo compounds are 2,2-azo-bis-isobutyronitrile, 2,2 '-azo-bis- (2,4-dimethyl-valeronitrile), 1,1'-azo-bis- (cyclohexanecarbonitrile) and 2,2' -azo-bis- (2,4-dimethyl-4-methoxyvaleronitrile).

25 Frie radikaler kan også dannes på anden måde, såsom ved bestråling med f.eks. røntgenstråler, elektronstråler og UV-stråling. Fremstilling af kontaktlinseråemner ved UV-stråling i nærværelse af en fotoinitiator, såsom diethoxy-acetophenon, 1-hydroxycyclohexylphenylketon, 2,2-dimethoxy-30 2-phenylacetophenon, phenothiazin, diisopropyl-xanthogen- disulfid, benzoin og benzoinderivater, er en foretrukket metode.Free radicals can also be formed by other means, such as by irradiation with e.g. X-rays, electron rays and UV rays. Preparation of contact lens blanks by UV radiation in the presence of a photoinitiator such as diethoxyacetophenone, 1-hydroxycyclohexylphenyl ketone, 2,2-dimethoxy-2-phenylacetophenone, phenothiazine, diisopropyl xanthogen disulfide, benzoin, and benzoin derivative, benzoin and benzoin derivative.

Initiatormængden kan variere fra 0,002 til 1 vægtprocent, 35 beregnet på monomeren og makromeren, men den ligger fortrins--is på 0,03 - 0,3 vægtprocent deraf.The amount of initiator may range from 0.002 to 1% by weight, based on the monomer and macromer, but it is preferably 0.03 to 0.3% by weight thereof.

En foretrukket laboratoriemetode til fremstilling af poly- 25A preferred laboratory method for preparing poly 25

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OISLAND

meren i form af en cylinder består i at fylde en fleksibel polymerrørform med den foretrukne sammensætning af makromer, monomerer og katalysator og omsætte blandingen i ca. 2 timer _ ved 80°C. Det færdige emne udtages ved, at rørformen skæres 5 op i længderetningen og trækkes af polymeremnet.the cylinder, in the form of a cylinder, consists of filling a flexible polymer tubular form with the preferred composition of macromers, monomers and catalyst and reacting the mixture for approx. 2 hours at 80 ° C. The finished workpiece is taken out by cutting the tubing 5 longitudinally and pulling from the polymer workpiece.

En anden foretrukken metode til fremstilling af polymeren består i bestråling med ultraviolet lys i nærværelse af en fotoinitiator og anvendelse af plaststøbeforme, der er transparente for UV-lys, f.eks. støbeforme fremstillet af poly-propylen.Another preferred method of preparing the polymer consists in ultraviolet light irradiation in the presence of a photoinitiator and the use of plastic molds that are transparent to UV light, e.g. molds made of polypropylene.

Omsætningen gennemføres fortrinsvis i en indifferent atmosfære, hvis den sker i åbne støbeforme. Det er kendt, at oxygen in- 1 u hiberer polymerisation og bevirker langvarige polymerisationstider. Hvis der anvendes lukkede støbeforme til fremstilling af artiklen, består støbeformene af indifferente materialer med lav oxygenpermeabilitet og ikke-klæbende egenskaber.The reaction is preferably carried out in an inert atmosphere if it occurs in open molds. Oxygen is known to inhibit polymerization and cause prolonged polymerization times. If closed molds are used to make the article, the molds consist of inert materials with low oxygen permeability and non-adhesive properties.

20 Eksempler på egnede støbeformsmaterialer er poly-(tetrafluor-ethylen), såsom "TEFLON"®, siliconekautsjuk, polyethylen, polypropylen og polyester, såsom "MYLAR"®. Glas- og metalstøbeforme kan anvendes, hvis der anvendes et egnet form-slip-middel.Examples of suitable molding materials are poly (tetrafluoroethylene) such as "TEFLON" ®, silicone rubber, polyethylene, polypropylene and polyester such as "MYLAR" ®. Glass and metal molds can be used if a suitable mold-release agent is used.

2525

De her omhandlede transparente og oxygenpermeable polymerer består af 8 - 70% af makromeren (A), der er copolymeriseret med 30 - 92% af vinylcomonomerkomponenten (B). 1 2 3 4 5 6The transparent and oxygen permeable polymers herein are comprised of 8 - 70% of the macromer (A) copolymerized with 30 - 92% of the vinyl comonomer component (B). 1 2 3 4 5 6

De her omhandlede polymerer kan tilpasses således, at de er 2 anvendelige enten som materiale til hårde kontaktlinser eller 3 som materiale til bløde kontaktlinser. Der kræves forskellige 4 comonomerer og forskellige polysiloxanmakromermængder for 5 at få optimal ydeevne i hver af kontaktlinsetyperne.The polymers herein can be adapted to be 2 usable either as hard contact lens material or 3 as soft contact lens material. Different 4 comonomers and different polysiloxane macromer volumes are required for 5 to achieve optimum performance in each of the contact lens types.

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2626

Ved valget af polysiloxankomponenten og vinylmonomeren til et hårdt kontaktlinsemateriale er det selvfølgeligt vigtigt at nå frem til en blanding, der giver klare polymerer med tilstrækkelig dimensionsstabilitet og oxygenpermeabilitet.Of course, in choosing the polysiloxane component and vinyl monomer for a hard contact lens material, it is important to arrive at a blend that provides clear polymers with sufficient dimensional stability and oxygen permeability.

5 Undertiden er en blanding af comonomerer fordelagtig med hensyn til undgåelse af faseadskillelse og derved opacitet.5 Sometimes a mixture of comonomers is advantageous in avoiding phase separation and thereby opacity.

Det er også lettere at opnå klare produkter med polysil-oxaner med relativ lav molekylvægt end med polysiloxaner med høj molekylvægt. Polysiloxaner med en kort kædelængde mellem 10 tværbindinger giver også hårdere, mere dimensionsstabile polymerer, men deres oxygenpermeabilitet er reduceret i sammenligning med polysiloxaner med længere kædelængde og følgelig lavere tværbindingstæthed. Ved et velovervejet valg af monomer (er) og polysiloxanmakromer er man således i stand 15 til at tilpasse de her omhandlede siliconepolymerers fysiske egenskaber og oxygenpermeabilitet i betydelig grad.It is also easier to obtain clear products with relatively low molecular weight polysiloxanes than with high molecular weight polysiloxanes. Polysiloxanes with a short chain length between 10 cross-links also produce tougher, more dimensionally stable polymers, but their oxygen permeability is reduced compared to longer chain length polysiloxanes and consequently lower cross-linking density. Thus, by a careful choice of monomer (s) and polysiloxane macromes, one is able to significantly adapt the physical properties and oxygen permeability of the silicone polymers in question.

Til fremstilling af hårde kontaktlinser omfatter den foretrukne polymer det tværbundne copolymerisationsprodukt af (A) fra 15 til 35 vægtprocent af en polysiloxan-20 makromer, og (B) fra 85 til 65 vægtprocent af en blanding af vanduopløselige monomerer (B^), af vandopløselige monomerer (B2) og af en diolefinisk monomer (Βχ) , idet B.j udgør fra 60 til 95%, B2 udgør fra 15 til 0%, og B udgør fra 25 til . 5%, beregnet på vægtprocent 25 af den totale vægt af monomerer. De foretrukne vanduopløselige monomerer er methylmethacrylat, isopropylmethacrylat, isobutylmethacrylat, tert.butylmethacrylat, cyclohexylmeth-acrylat, isobornylmethacrylat 'eller blandinger deraf. De foretrukne vandopløselige monomerer B2 er 2-hydroxyethyl-30 methacrylat, Ν,Ν-dimethylacrylamid, acrylsyre, methacryl- syre eller N-vinyl-2-pyrrolidon eller blandinger deraf. Den foretrukne diolefiniske monomer B er neopentylenglycol- Λ diacrylat, ethylenglycoldimethacrylat eller reaktionsproduktet af 1 mol isophorondiisocyanat og 2 mol 2-hydroxyethyl-35 methacrylat.For the preparation of hard contact lenses, the preferred polymer comprises the crosslinked copolymerization product of (A) from 15 to 35% by weight of a polysiloxane macromer, and (B) from 85 to 65% by weight of a mixture of water-insoluble monomers (B monomers (B2) and of a diolefinic monomer (Βχ), with Bj being from 60 to 95%, B2 being from 15 to 0%, and B being from 25 to. 5%, by weight of 25% of the total weight of monomers. The preferred water-insoluble monomers are methyl methacrylate, isopropyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate or mixtures thereof. The preferred water-soluble monomers B2 are 2-hydroxyethyl methacrylate, Ν, Ν-dimethylacrylamide, acrylic acid, methacrylic acid or N-vinyl-2-pyrrolidone or mixtures thereof. The preferred diolefinic monomer B is neopentylene glycol Λ diacrylate, ethylene glycol dimethacrylate or the reaction product of 1 mole of isophorone diisocyanate and 2 moles of 2-hydroxyethyl methacrylate.

2727

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Til fremstilling af bløde kontaktlinser indeholder den fore-* trukne polymer det tværbundne copolymerisationsprodukt af (A) fra 40 til 60 vægtprocent af en polysiloxan-makromer, og (B) fra 60 til 40 vægtprocent af en 5 blanding af vanduopløselige monomer (B^), vandopløselige monomer (B2) og en diolefinisk monomer (Βχ), hvor B^ udgør fra 75 til 100%, B2 udgør fra 25 til 0%, og Βχ udgør fra 5 til 0%, beregnet på vægtprocent af den totale vægt af monomerer. De foretrukne vanduopløselige 10 monomerer (B^) er ethylacrylat eller -methacrylat, n-butyl- acrylat eller -methacrylat, n-hexylacrylat eller -methacrylat, 2-ethylhexylacrylat eller -methacrylat, n-octylacrylat eller -methacrylat, n-decylacrylat eller -methacrylat eller blandinger deraf eller blandinger med methyl- eller isobornyl-15 methacrylat. De foretrukne vandopløselige monomerer (B2) og diolefiniske monomerer (B„) er sådanne, som er omtalt oven- Λ for til fremstilling af hårde kontaktlinser.For the preparation of soft contact lenses, the preferred polymer contains the cross-linked copolymerization product of (A) from 40 to 60% by weight of a polysiloxane macromer, and (B) from 60 to 40% by weight of a 5 mixture of water-insoluble monomer (B , water-soluble monomer (B2) and a diolefinic monomer (Βχ), where B B is from 75 to 100%, B2 is from 25 to 0%, and Βχ is from 5 to 0%, by weight of the total weight of monomers . The preferred water-insoluble monomers (B 1) are ethyl acrylate or methacrylate, n-butyl acrylate or methacrylate, n-hexyl acrylate or methacrylate, 2-ethylhexyl acrylate or methacrylate, n-octyl acrylate or methacrylate, n-decylate methacrylate or mixtures thereof or mixtures of methyl or isobornyl methacrylate. The preferred water-soluble monomers (B2) and diolefinic monomers (B „) are those mentioned above for the preparation of hard contact lenses.

Et eksempel på en foretrukket polymer til fremstilling af en hård kontaktlinse indeholder (A) 30 vægtprocent polysil-20 oxan med strukturen A2, hvor R4 betyder et diradikal afledt af isophorondiisocyanat, og Z2 hver især betyder -O-, og y2 er 2, og 70 vægtprocent monomer (B), hvor B1 er 71,4% methylmethacrylat, B2 er 5,7% 2-hydroxyethyl-methacrylat, og B er 22,9% neopentylenglycoldiacrylat, be-An example of a preferred polymer for producing a hard contact lens contains (A) 30% by weight of polysiloxane of structure A2, wherein R4 is a diradical derived from isophorone diisocyanate and Z2 is each -O- and y2 is 2 and 70% by weight of monomer (B), where B1 is 71.4% methyl methacrylate, B2 is 5.7% 2-hydroxyethyl methacrylate, and B is 22.9% neopentylene glycol diacrylate;

XX

25 regnet på vægtprocent totale monomerer.25, by weight of total monomers.

Et eksempel på en foretrukket polymer til fremstilling af en blød kontaktlinse indeholder (A) 50 vægtprocent polysiloxan med strukturen A2, hvor betyder et diradikal, der stammer fra isophorondiisocyanat, Z-j og Z2 hver især betyder 30 -O-, og y2 er 2, og 50 vægtprocent monomerer (B), hvor B^ er 80% af en 50:50-blanding af methylmethacrylat og 2-ethylhexylacrylat, og B2 er 20% 2-hydroxyethylmethacrylat.An example of a preferred polymer for making a soft contact lens contains (A) 50% by weight of polysiloxane of structure A2, where a diradical derived from isophorone diisocyanate, Zj and Z2 each means 30 -O-, and y2 is 2, and 50% by weight of monomers (B), wherein B 2 is 80% of a 50:50 mixture of methyl methacrylate and 2-ethylhexyl acrylate, and B2 is 20% 2-hydroxyethyl methacrylate.

Selv om den foreliggende opfindelse først og fremmest angår fremstillingen af hårde, dimensionsstabile kontaktlinser,Although the present invention is primarily concerned with the manufacture of hard, dimensionally stable contact lenses,

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28 ligger det inden for opfindelsens rammer at anvende en hvilken som helst af ovennævnte monomerer til fremstilling af stærke, 02-permeable polymerer med et bredt område af fysiske egenskaber, fra hårde og stive til kautsjukagtige og 5 bløde. Sådanne bløde polymerer er f.eks. anvendelige som bandager eller som bløde kontaktlinser, især når de behandles ved en vilkårlig af de almindeligt anvendte metoder, der anvendes til forøgelse af befugteligheden af hydrofobe overflader, såsom plasmabehandling og bestrålingstransplantation 10 og oxidation.28, it is within the scope of the invention to use any of the above monomers to produce strong, O 2-permeable polymers with a wide range of physical properties, from hard and rigid to rubbery and soft. Such soft polymers are e.g. useful as bandages or as soft contact lenses, especially when treated by any of the commonly used methods used to increase the wettability of hydrophobic surfaces, such as plasma treatment and radiation transplantation and oxidation.

På grund af deres gode vævsforenelighed og oxygenpermeabili-tet samt styrke og elasticitet er de her omhandlede polymerer særlig egnede til anvendelse som intramuskulære og subcutane implantater i varmblodede dyr og som kontaktlinsemateriale.Because of their good tissue compatibility and oxygen permeability, as well as strength and elasticity, the polymers herein are particularly suitable for use as intramuscular and subcutaneous implants in warm blooded animals and as contact lens material.

15 Af samme grund kan de her omhandlede materialer tilpasses til substituerede blodkar eller anastomoser uden for legemet.For the same reason, the materials of this invention may be adapted to substituted blood vessels or anastomoses outside the body.

Opfindelsen illustreres nærmere i de følgende eksempler.The invention is further illustrated in the following examples.

I eksemplerne bestemmes den specifikke oxygen-20 permeabilitet (02.DK) ved måling af permeabilitet for opløst oxygen ved 35°C med en polarografisk elektrode i et luft-mættet vandigt miljø, og den udtrykkes i enheder o2dk = 0111 (STp)x.cm x 1010 cm xsekxcmHgIn the examples, the specific oxygen permeability (02.DK) is determined by measuring dissolved oxygen permeability at 35 ° C with a polarographic electrode in an air-saturated aqueous environment and it is expressed in units o2dk = 0111 (STp) x. cm x 1010 cm xsekxcmHg

Befugteligheden bestemmes ved måling af kontaktvinklen for en 25 lille dråbe n-octan, der er steget op til den nedre overflade af et 1 mm tykt prøveark, der er neddyppet i octanmættet, destilleret vand ved 36°C. Ved denne måling tilkendegiver høje tal høj befugtelighed.The wettability is determined by measuring the contact angle of a small drop of n-octane that has risen to the lower surface of a 1 mm thick sample sheet immersed in octane-saturated distilled water at 36 ° C. By this measurement, high numbers indicate high humidity.

Hårdheden bestemmes under anvendelse af et Shore-D durometerThe hardness is determined using a Shore-D durometer

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29 på polerede overflader af.centerskårne skiver med en diameter på 10 mm og en højde på 8 mm.29 on polished surfaces of center cut discs with a diameter of 10 mm and a height of 8 mm.

Eksempel 1Example 1

Fremstilling af polysiloxanmakromer 5 En 1 liters, trehalset kolbe, der er udstyret med en mekanisk omrører, termometer, svalerør og nitrogentilgang, chargeres med 186,6 g (0,03 mol) polydimethylsiloxan-triol (Dow Corning, væske 1248), der er blevet befriet for flygtige forbindelser ved gennemledning gennem en såkaldt "wiped 10 film" fordamper. Dernæst tilsættes 21,0 g (0,0945 mol) 1-isocvanatmethyl-5-isocyanat-1,3,3-trimethylcyclohexan (isophorondiisocyanat, IPDI) sammen med 0,025 g dibutyl-tindilaurat som katalysator. Blandingen omrøres derpå under nitrogen på et temperaturreguleret vandbad ved 50°c i 5 ti-15 mer. På dette tidspunkt er NCO-indholdet faldet til 1,94% (2,00% ifølge teorien), bestemt ved titrering.Preparation of polysiloxane macromes 5 A 1 liter, three-neck flask equipped with a mechanical stirrer, thermometer, condenser and nitrogen supply is charged with 186.6 g (0.03 mole) of polydimethylsiloxane triol (Dow Corning, liquid 1248) which is been freed of volatile compounds by passage through a so-called "wiped 10 film" evaporator. Next, 21.0 g (0.0945 mol) of 1-isocvanate methyl-5-isocyanate-1,3,3-trimethylcyclohexane (isophorone diisocyanate, IPDI) is added together with 0.025 g of dibutyltin dililate as catalyst. The mixture is then stirred under nitrogen on a temperature-controlled water bath at 50 ° C for 5 hours. At this point, the NCO content has dropped to 1.94% (2.00% according to theory), as determined by titration.

Derefter fortyndes 169,4 g af den ovenfor fremstillede poly-dimethylsiloxantriisocyanatpræpolymer med 10,2 g 2-hydroxy-ethylmethacrylat (HEMA) og omrøres under nitrogen ved stue-20 temperatur, indtil alle NCO-grupper er omsat, bestemt ved fraværelsen af isocyanatbåndet i det infrarøde spektrum.Then 169.4 g of the above-prepared poly-dimethylsiloxane triisocyanate prepolymer are diluted with 10.2 g of 2-hydroxyethyl methacrylate (HEMA) and stirred under nitrogen at room temperature until all NCO groups are reacted, determined by the absence of the isocyanate band in the infrared spectrum.

Det fremkomne produkt består af >99,9% methacrylat-afsluttet polysiloxan og en mindre mængde HEMA-maskeret IPDI, hvilket indikerer, at der er sket en vis kædeforlængelse.The resulting product consists of> 99.9% methacrylate-terminated polysiloxane and a minor amount of HEMA-masked IPDI, indicating that some chain elongation has occurred.

25 Dette bekræftes også af gelpermeationschromatografi.This is also confirmed by gel permeation chromatography.

Eksempel 2-17Examples 2-17

Fremstilling af polymerprøver 30 g af i hvert tilfælde af den ifølge eksempel 1 fremstillede polysiloxanmakromer blandes med comonomerer i det iPreparation of Polymer Samples 30 g of each case of the polysiloxane macromer produced in Example 1 are mixed with comonomers in the

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30 tabel I viste forhold. 0,06 g (0,2%) 1-hydroxycyclohexyl-phenylketon (UV-initiator A) tilsættes, og hver blanding af-gasses omhyggeligt og opbevares dernæst under nitrogen. En portion af hver blanding anvendes til fremstilling af 0,1 mm 5 tykke film mellem silanbehandlede glasplader. Der anvendes 0,1 mm tyk "MYLAR"® (polyesterfilm fra DuPont) som afstandsstykke, og formen holdes sammen med klemmer. Formene eksponeres med UV-lys fra en "Black Light Blue"-lampe ("SYLVANIA"®) i 3 timer, hvorefter polymeren fjernes fra formen for at 10 blive anvendt til oxygenpermeabilitetsmålinger.30 Table I. 0.06 g (0.2%) of 1-hydroxycyclohexyl-phenyl ketone (UV initiator A) is added and each mixture is carefully degassed and then stored under nitrogen. A portion of each mixture is used to make 0.1 mm thick films between silane treated glass sheets. 0.1 mm thick "MYLAR" ® (DuPont polyester film) is used as spacer and the mold is held together with clamps. The molds are exposed to UV light from a "Black Light Blue" lamp ("SYLVANIA" ®) for 3 hours, after which the polymer is removed from the mold to be used for oxygen permeability measurements.

På samme måde udstøbes en 1 mm tyk plade fra hver monomer--makromerblanding til anvendelse til bestemmelse af befugtelighed .Similarly, a 1 mm thick plate is cast from each monomer - macromer mixture for use in determining wettability.

Endnu en anden del af hver monomer-makromerblanding fyldes ved hjælp af en sprøjte med fast volumen i cylindriske poly-15 propylenforme med en diameter på 14 mm og en højde på 8 mm og lukkes med et løstsluttende, konvekst polypropylenlåg.Yet another portion of each monomer macromer mixture is filled by means of a fixed volume syringe in cylindrical polypropylene molds having a diameter of 14 mm and a height of 8 mm and closed with a loosely fitting, convex polypropylene lid.

Formene indsættes i en bakke og bestråles i en nitrogenskyllet kasse under anvendelse af de ovenfor beskrevne lamper, først nedefra, indtil blandingen er gelatineret (15 mi-20 nutter) , derpå fraoven og franeden i i alt 3 timer. Derefter åbnes formene, og polymerskiven udtages. Adskillige skiver skæres i to, såvel parallelt med som vinkelret på den runde overflade, og de skårne flader slibes til måling af hårdheden.The molds are inserted into a tray and irradiated in a nitrogen-rinsed box using the lamps described above, first from below, until the mixture is gelatinized (15 minutes), then top and bottom for a total of 3 hours. Then the molds are opened and the polymer disc is removed. Several slices are cut in two, both parallel to and perpendicular to the round surface, and the cut surfaces are sanded to measure the hardness.

Værdierne i nedenstående tabel viser de udvalgte comonome-25 rers virkning på O2.DK, befugtelighed og hårdhed. Disse polymerer har Young's Modulus-værdier på >1 (GPa) .The values in the table below show the effect of the selected comonomers on O2.DK, humidity and hardness. These polymers have Young's Modulus values of> 1 (GPa).

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31 & I T) O Q <1) I x31 & I T) O Q <1) I x

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GG

O d' —* g C - m o λ ^ ocMocovooro-d1 cg cm q __ 3 Ό Oi 4 * ^h'*·»····»·'' * * * OM OOOCMr- I t- I r-*-T-r-T-r-r-x- τ-τ- τ- φ s: — φ ρ er· c •Η o o iH o i h o i p ·> <U M ,y i—i v; n, Gi'nidJinoT-woo^r^o^M^oin t'-CM cmO d '- * g C - mo λ ^ ocMocovooro-d1 cg cm q __ 3 Ό Oi 4 * ^ h' * · »····» · '' * * * OM OOOCMr- I t- I r- * -TrTrrx- τ-τ- τ- φ s: - φ ρ is · c • Η oo iH oihoip ·> <UM, yi — iv; n, Gi'nidJinoT-woo ^ r ^ o ^ M ^ oin t'-CM cm

tø p ιί·β^Μ mNfOrt-Orr^CMrtMr CMr- COthaw p ιί · β ^ Μ mNfOrt-Orr ^ CMrtMr CMr- CO

Min P G C G T-T-r-T-v-T-r-r-r-r-v-r- O ffi O Π3 O Ή 4-! > O > Ai >My P G C G T-T-r-T-v-T-r-r-r-r-v-r- O fi O Π3 O Ή 4-! > O> Ai>

cK> McK> M

vo QJ _ \p q ποο'τΓ'ΝΜΜ'ι-οογ'Ί'Ν m o ro J_| . *.·. *> φ f\J *31 r— CO CO O CO r- CM ΟΊ CO Γ~· 00 CM Or- Γ~-vo QJ _ \ p q ποο'τΓ'ΝΜΜ'ι-οογ'Ί'Ν m o ro J_ | . *. ·. *> φ f \ J * 31 r— CO CO O CO r- CM ΟΊ CO Γ ~ · 00 CM Or- Γ ~ -

rf-H O CMrOCOCOfOCOCOinCMCOCO'rJ’rO CO *J< CMrf-H O CMrOCOCOfOCOCOinCMCOCO'rJ'rO CO * J <CM

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Nedenstående eksempler viser polysiloxanmakromerindholdets virkning på O2.DK og befugtelighed.The following examples show the effect of polysiloxane macromer content on O2.DK and wettability.

Eksempel 18 ?- 26Examples 18 - 26

Onder anvendelse af den i ovenstående eksempel 2-17 beskrevne 5 fremgangsmåde blandes den i eksempel 1 fremstillede makromer med forskellige mængder monomerer som angivet i tabel II, og blandingen polymeriseres til 0,1 mm og 1,0 mm tykke film. Polymererne afprøves for oxygenpermeabilitet og befugtelig-hed som beskrevet.Using the procedure described in Examples 2-17 above, the macromers prepared in Example 1 are mixed with different amounts of monomers as set forth in Table II and the mixture is polymerized into 0.1 mm and 1.0 mm thick films. The polymers are tested for oxygen permeability and wettability as described.

10 Tabel IITable II

Virkning af % polysiloxanmakromer (Si-Mak) på fysiske egenskaberEffect of% polysiloxane macromes (Si-Mak) on physical properties

Eks. Sammensætning (%) 1_ Octan/vand- nr. Si-Mak MMA CYMA HEMA 02.DK kontaktvinkel, ° 18 8 91 - 1 1,1 100 19 16 87 - 2 7,8 122 15 20 24 73 - 3 17 122 21 32 · 64 4 21 124 22 40 55 - 5 57 146 23 48 46 - 6 69 146 24 24 - 73 3 8 100 20 25 32 - 64 4 17 116 26 40 - 55 5 34 121 MMA er methylmethacrylat CYMA er cyclohexylmethacrylat HEMA er 2-hydroxyethylmethacrylatEx. Composition (%) 1_ Octane / water no. Si-Mak MMA CYMA HEMA 02.DK contact angle, ° 18 8 91 - 1 1.1 100 19 16 87 - 2 7.8 122 15 20 24 73 - 3 17 122 21 32 · 64 4 21 124 22 40 55 - 5 57 146 23 48 46 - 6 69 146 24 24 - 73 3 8 100 20 25 32 - 64 4 17 116 26 40 - 55 5 34 121 MMA is methyl methacrylate CYMA is cyclohexyl methacrylate HEMA is 2-hydroxyethyl methacrylate

Eksempel 27 - 29Examples 27 - 29

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Nedenstående eksempler viser virkningen af anvendelse af en hydrofil comonomer (dimethylacrylamid). De i eksempel 18-26 beskrevne fremgangsmåder følges.The following examples show the effect of using a hydrophilic comonomer (dimethyl acrylamide). The procedures described in Examples 18-26 are followed.

Octan/- Vandindhold - vand- ved kvæld- 5 Eks. Si-Mak Comonomer HEMA DMA* C^.DK kontakt- ning til nr._I_%_% %_vinkel·,0 ligevægt (%) 27 32 MMA 54 4 10 35 111 5,7 28 32 CYMA 54 4 10 36 120 2,0 29 32 CYMA 54 4 20 34 117 6,7 *DMA er dimethylacrylamid.Octane / - Water content - water at night- 5 Ex. Si-Mak Comonomer HEMA DMA * C ^ .DK connection to No._I _% _%% _ angle ·, 0 equilibrium (%) 27 32 MMA 54 4 10 35 111 5.7 28 32 CYMA 54 4 10 36 120 2 0 29 32 CYMA 54 4 20 34 117 6.7 * DMA is dimethyl acrylamide.

10 Eksempel 30 - 34Examples 30 - 34

Nedenstående eksempler viser yderligere tværbindingsmidlers virkning på O2.DK, befugtelighed og hårdhed.The following examples further illustrate the effect of crosslinking agents on O2.DK, wettability and hardness.

Idet der gås frem på den i eksempel 2-17 beskrevne måde, blandes den i eksempel 1 fremstillede makromer med comono-15 merer i de i nedenstående tabel viste forhold. Blandingerne polymeriseres og afprøves som beskrevet.Proceeding in the manner described in Examples 2-17, the macromers prepared in Example 1 are mixed with comonomers in the ratios shown in the table below. The mixtures are polymerized and tested as described.

Sammensætning* Octan/ -2- vand-Composition * Octane / -2- water

Eks. Si-Mak Comonomerer, % HEMA Oj.DK kontakt- Shore-D- nr._%_%_vinkel -hårdhed 30 30 MMA 50 NPDA 16 4 37,7 124 78 31 30 MMA 41 NPDA 25 4 34,4 131 82 20 32 30 CYMA 50 NPDA 16 4 27,5 125 78 33 30 IBMA 50 NPDA 16 4 31,8 120 82 34 30 IBMA 25 EGDA 16 4 33,4 122 77 CYMA 25 *IBMA er isobutylmethacrylat NPDA er neopentylenglycoldiacrylat 25 EGDA er ethylenglycoldimethacrylatEx. Si-Mak Comonomers,% HEMA Oj.DK contact- Shore-D No._% _% _ angle-hardness 30 30 MMA 50 NPDA 16 4 37.7 124 78 31 30 MMA 41 NPDA 25 4 34.4 131 82 20 32 30 CYMA 50 NPDA 16 4 27.5 125 78 33 30 IBMA 50 NPDA 16 4 31.8 120 82 34 30 IBMA 25 EGDA 16 4 33.4 122 77 CYMA 25 * IBMA is isobutyl methacrylate NPDA is neopentylene glycol diacrylate 25 EGDA is ethylene glycol dimethacrylate

Eksempel 35 - 38Examples 35 - 38

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Fremgangsmåden ifølge eksempel 1 gentages, idet dog mængden af isophorondiisocyanat (IPDI) forøges fra 0,0945 mol (svarende til et 5% molært overskud af NCO/OH) til 5 0,105 (16,7% molært overskud af NCO) - Eks. nr. 35 0,166 (84,4% molært overskud af NCO) - Eks. nr. 36 0,243 (170.0% molært overskud af NCO)- Eks. nr. 37 0,335 (272,2% molært overskud af NCO)- Eks. nr. 38The procedure of Example 1 is repeated, however, the amount of isophorone diisocyanate (IPDI) is increased from 0.0945 mol (corresponding to a 5% molar excess of NCO / OH) to 5 0.105 (16.7% molar excess of NCO) - Ex. No. 35 0.166 (84.4% molar excess of NCO) - Ex. No. 36 0.243 (170.0% molar excess of NCO) - Ex. No. 37 0.335 (272.2% molar excess of NCO) - Ex. No. 38

Efter omsætning af den NCO-afsluttede præpolymer med ΗΕΜΆ 10 fås en blanding af 30 dele methacrylat-afsluttet polysiloxan, 4 dele ΗΕΜΆ og 1, 5, 10 og 16 dele af reaktionsproduktet af 2 mol HEMA og 1 mol IPDI (IPDI-diHEMA), bestemt ved gelper-meationschromatografi.After reaction of the NCO-terminated prepolymer with ΗΕΜΆ 10, a mixture of 30 parts of methacrylate-terminated polysiloxane, 4 parts ΗΕΜΆ and 1, 5, 10 and 16 parts of the reaction product of 2 moles of HEMA and 1 mole of IPDI (IPDI-diHEMA) is obtained. determined by gelper-meation chromatography.

Blandingerne fortyndes med methylmethacrylat og udstøbes i 15 form af klare skiver, . plader og film.med følgende egenskaber:The mixtures are diluted with methyl methacrylate and cast in the form of clear slices. plates and films.with the following properties:

Sammensætning, %_ Octan/- vand-Composition,% _ Octane / - water

Eks. IPDI- O-.DK kontakt- Shore-D- nr. Si-Mak MMA HEMA di HEMA_vinkel -hårdhed 35 36 65 4 1 26,5 126 79 36 30 61 4 5 25,6 117 81 20 37 30 56 4 10 26,2 121 79 38 30 50 4 16 25,4 112 77Ex. IPDI- O-.DK contact- Shore-D No. Si-Mak MMA HEMA di HEMA_vinkel hardness 35 36 65 4 1 26,5 126 79 36 30 61 4 5 25,6 117 81 20 37 30 56 4 10 26 , 2 121 79 38 30 50 4 16 25,4 112 77

Nedenstående eksempler påviser anvendeligheden af polysil-oxan-urethan-methacrylatet ved fremstilling af klare og bløde, oxygenpermeable polymerer (med et Young's Modulus 25 <1) til anvendelse som bløde kontaktlinser.The following examples demonstrate the utility of the polysiloxane-urethane methacrylate in the preparation of clear and soft, oxygen-permeable polymers (with a Young's Modulus 25 <1) for use as soft contact lenses.

Eksempel 39 - 44Examples 39 - 44

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Polysiloxanmakromeren ifølge eksempel 1 fortyndes med forskellige comonomerer og 0,1% UV-initiator A og polymeriseres ved eksponering med UV-lys som beskrevet i eksempel 2-17.The polysiloxane macromer of Example 1 is diluted with various comonomers and 0.1% UV initiator A and polymerized by exposure to UV light as described in Examples 2-17.

5 Sammensætningerne og egenskaberne er angivet nedenfor.5 The compositions and properties are listed below.

Sammensætning_ Octan/-Composition_ Octane / -

Si-Mak Comonomer % Young's vand-Si-Mak Comonomer% Young's water-

Eks. % Methacrylat Udseende O2.DK Modulus kontakt- nr._Estere_Følelse_(GPa) vinkel 39 30 n-butyl- 66 klar 39 0,7 130 blød 40 30 n-hexyl- 66 klar 39 0,3 136 blød 41 30 n-octyl- 66 klar 38 <1θ“3 92 blød 10 42 30 sek.butyl- 66 klar 29 0,8 124 blød 43 30 2-ethylhexyl- 66 klar 32 <1θ”3 115 blød 44 30 pentamethyldi- klar 43 1,0 122 siloxanyl- blød propyl 33: +methyl-(1:) 33Ex. % Methacrylate Appearance O2.DK Modulus Contact No._Esters_Feel_ (GPa) Angle 39 30 n-Butyl 66 Clear 39 0.7 130 Soft 40 30 N-Hexyl 66 Clear 39 0.3 136 Soft 41 30 N-Octyl 66 clear 38 <1θ “3 92 soft 10 42 30 sec.butyl- 66 clear 29 0.8 124 soft 43 30 2-ethylhexyl- 66 clear 32 <1θ” 3 115 soft 44 30 pentamethyldi- clear 43 1.0 122 siloxanyl - soft propyl 33: + methyl- (1 :) 33

Eksempel 45 - 48Examples 45 - 48

Polysiloxanmakromeren ifølge eksempel 1 fortyndes med forskel-15 lige comonomerer og 0,2% UV-initiator A og polymeres ved eksponering med UV-lys som beskrevet i eksempel 2-17. Der fås klare polymerer, hvis sammensætning og egenskaber er angivet nedenfor:The polysiloxane macromer of Example 1 is diluted with various comonomers and 0.2% UV Initiator A and polymerized by exposure to UV light as described in Examples 2-17. Clear polymers are available whose composition and properties are listed below:

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Eks. Sammensætning_%_ Octan/vand- nr. Si-Mak Hema Comonomerer* kontaktvinkel 45 50 10 Methyl-MA 40 66 135 46 50 10 Methyl-MA 20 99 143 2-Ethylhexyl-A 20 47 50 10 2-Ethylhexyl-A 20 83 138 +Glycidyl-MA 20 5 48 60 - 2-Ethylhexyl-A 20 89 141 +Glycidyl-MA 20 *MA: methacrylat, A: acrylat.Ex. Composition _% _ Octane / Water No. Si-Mak Hema Comonomers * Contact Angle 45 50 10 Methyl MA 40 66 135 46 50 10 Methyl MA 20 99 143 2-Ethylhexyl-A 20 47 50 10 2-Ethylhexyl-A 20 83 138 + Glycidyl-MA 20 5 48 60 - 2-Ethylhexyl-A 20 89 141 + Glycidyl-MA 20 * MA: methacrylate, A: acrylate.

Nedenstående eksempler illustrerer anvendeligheden af andre aktivt—hvdrogenholdige monomerer end HEMA til fremstilling af polysiloxanpræpolvmeren.The following examples illustrate the utility of active-hydrogen-containing monomers other than HEMA in the preparation of the polysiloxane prepolymer.

10 Eksempel 49 - 55Examples 49 - 55

Fremgangsmåden ifølge eksempel 1 gentages, idet der dog i stedet for HEMA anvendes de ækvivalente mængder af andre aktivt hydrogen-holdige vinylmonomerer til maskering i endestillingen af den NCO-afsluttede polysiloxanpræpolymer. .The procedure of Example 1 is repeated, however, instead of HEMA, the equivalent amounts of other active hydrogen-containing vinyl monomers are used for masking in the end position of the NCO-terminated polysiloxane prepolymer. .

15 Slutmaskeringstrinets afslutning verificeres ved IR-spektro-skopi. På denne måde fremstilles nedenstående vinyl-afsluttede polysiloxaner som klare, viskose væsker.The end of the final masking step is verified by IR spectroscopy. In this way, the following vinyl-terminated polysiloxanes are prepared as clear, viscous liquids.

Eks. nr. Aktivt-H-holdig vinylmonomer_ForkortelseEx. No. Active-H-containing vinyl monomer_ Abbreviation

49 2-Hydroxyethvlacrylat HEA49 2-Hydroxyethyl acrylate HEA

20 50 2-Hydroxypropylacrylat HPA20 2-Hydroxypropyl Acrylate HPA

51 4-Hydroxybutylvinylether HBVE51 4-Hydroxybutylvinyl ether HBVE

52 3-Hydroxypropylbuty1fumarat HPBF52 3-Hydroxypropylbutyl fumarate HPBF

53 Tert.butylaminoethylmethacrylat BAEM53 Tert.butylaminoethyl methacrylate BAEM

54 Ally1alkohol ARA54 Ally1 alcohol ARA

25 55 Methallylalkohol MALA55 55 Methallyl alcohol MALA

Nedenstående eksempler illustrerer anvendeligheden af poly-The following examples illustrate the utility of polyethylene

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37 siloxaner med methacrylyl-, vinylether- og fumarat-umætning ved fremstilling af klare, hårde og C^-permeable polymerer.37 siloxanes with methacrylyl, vinyl ether and fumarate unsaturation in the preparation of clear, hard and C C-permeable polymers.

Eksempel 56 - 60Examples 56 - 60

De vinylafsluttede polysiloxaner ifølge eksempel 45 - 47 for-5 tyndes med monomerer og polymeriseres i form af klare film og knapper under anvendelse af en 0,02% UV-initiator A som initiator. Sammensætningerne og deres fysiske egenskaber er angivet i nedenstående tabel.The vinyl-terminated polysiloxanes of Examples 45-47 are diluted with monomers and polymerized in the form of clear films and buttons using a 0.02% UV Initiator A as initiator. The compositions and their physical properties are given in the table below.

Eks. Polydimethylsiloxan % Shore-D- nr. maskeret med* Comonomerer % O2.DK -hårdhed 10 56 BAEM (Eks. 53) 33 Cyclohexyl- 67 19,4 77 methacrylat 57 BAEM (Eks. 53) 33 Methyl- 67 31,3 79 methacrylat 58 BAEM (Eks. 53) 33 Vinylacetat 67 92,0 60 59 HBVE (Eks. 51) 33 Vinylacetat 67 20,6 83 60 HPBF (Eks. 52) 16 Vinylacetat 40 10,5 80Ex. Polydimethylsiloxane% Shore-D No. Masked with * Comonomers% O2.DK Hardness 10 56 BAEM (Ex. 53) 33 Cyclohexyl 67 19.4 77 Methacrylate 57 BAEM (Ex. 53) 33 Methyl 67 31.3 79 methacrylate 58 BAEM (Ex. 53) 33 Vinyl Acetate 67 92.0 60 59 HBVE (Ex. 51) 33 Vinyl Acetate 67 20.6 83 60 HPBF (Ex. 52) 16 Vinyl Acetate 40 10.5 80

Dimethyl-maleat 30Dimethyl maleate 30

Cyclohexyl-methacrylat 7 HPBF 7 15 * Jvf. Eks. 49-55 med hensyn til forkortelserne.Cyclohexyl methacrylate 7 HPBF 7 15 Cf. Ex. 49-55 with regard to the abbreviations.

Eksempel 61Example 61

Ved den i eksempel 1 beskrevne fremgangsmåde maskeres poly-dimethylsiloxantriol (Dow Corning, væske 1248) i endestilling med isophorondiisocyanat. Et 10% molært overskud af meth-acrylsyre tilsættes sammen med 0,05% cobaltnaphthenat. Der udvikles C02, og blandingen holdes ved 50°C i 6 timer, hvorefter den procentvise NCO-værdi er faldet til næsten nul. Blandingen fortyndes med 70% methvlmethacrylat. 0,1% UV-initiator A tilsættes, og der fremstilles polymerplader og -film som beskrevet i eksempel 2. Polymeren er uklar-hvid, har en O2.DK-In the procedure described in Example 1, poly-dimethylsiloxanthriol (Dow Corning, liquid 1248) is masked in end position with isophorone diisocyanate. A 10% molar excess of methacrylic acid is added together with 0.05% cobalt naphthenate. CO 2 is developed and the mixture is maintained at 50 ° C for 6 hours, after which the percent NCO value has dropped to almost zero. The mixture is diluted with 70% methyl methacrylate. 0.1% UV initiator A is added and polymer plates and films are prepared as described in Example 2. The polymer is cloudy white, has an O

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38 -værdi på 68 og en octan/vandkontaktvinkel på 103°.38 value of 68 and an octane / water contact angle of 103 °.

Eksempel 62 På den i eksempel 1 og 2 beskrevne måde fremstilles en polymer, idet der anvendes 2,2,4(2,4,4)-trimethylhexan-1,6-di-5 isocyanat i stedet for IPDI. Der fremkommer en polymer med egenskaber, der er praktisk taget identiske med egenskaberne af polymeren ifølge eksempel 2.Example 62 In the manner described in Examples 1 and 2, a polymer is prepared using 2,2,4 (2,4,4) trimethylhexane-1,6-di-isocyanate instead of IPDI. A polymer is obtained having properties that are virtually identical to the properties of the polymer of Example 2.

Nedenstående eksempler viser anvendeligheden af fluorerede comonomerer ved fremstilling af de her omhandlede, klare, 10 oxygenpermeable polymerer.The following examples illustrate the utility of fluorinated comonomers in the preparation of the present clear, 10 oxygen permeable polymers.

Eksempel 63 - 68 På den i eksempel 1 og 2 beskrevne måde fremstilles nedenstående polymerer, og deres oxygenpermeabilitet måles. Forkortelsen MA i den fluorerede comonomer betyder methacrylat.Examples 63 - 68 In the manner described in Examples 1 and 2, the following polymers are prepared and their oxygen permeability measured. The abbreviation MA in the fluorinated comonomer means methacrylate.

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Nedenstående eksempel viser, at klarheden af polymererne ifølge eksempel 63 - 68 er et uventet resultat, fordi analoge materialer, der ikke indeholder silicone, giver uforenelige blandinger og svage, opake polymerer.The following example shows that the clarity of the polymers of Examples 63-68 is an unexpected result because analogous materials that do not contain silicone give incompatible mixtures and weak opaque polymers.

5 Eksempel 69Example 69

Eksempel 63 gentages, men siloxan-makromeren ifølge eksempel 1 erstattes med en analog makromer, der er fremkommet ved omsætning af 1 mol polytetramethylenoxid-diol (molekylvægt 2000} med 2 mol isophorondiisocyanat efterfulgt af maske-10 ring i endestilling med overskud af HEMA. Der fremkommer en uforenelig blanding, der skiller sig i faser ved henstand og under polymerisation. Den fremkomne polymerplade er opak, skrøbelig og meget svag.Example 63 is repeated, but the siloxane macromer of Example 1 is replaced by an analog macromer obtained by the reaction of 1 mole of polytetramethylene oxide diol (molecular weight 2000} with 2 moles of isophorone diisocyanate followed by masking in the final position with excess HEMA. an incompatible mixture which differs in phases upon standing and during polymerization The resulting polymer plate is opaque, fragile and very weak.

Nedenstående eksempler illustrerer anvendelsen af andre poly-15 siloxaner ved fremstillingen af de her omhandlede polymerer.The following examples illustrate the use of other polysiloxanes in the preparation of the polymers herein.

Eksempel 70 På den i eksempel 1 beskrevne måde omsættes 21,7 g (0,025 mol) polydimethylsiloxan-diol (Dow Corning, væske Q4-3557) med 11,7 g (0,0526 mol) isophorondiisocyanat. Efter omrøring 20 under nitrogen i 5 timer ved 50°C falder NCO-indholdet til 6,80% (6,90% ifølge teorien)Example 70 In the manner described in Example 1, 21.7 g (0.025 mole) of polydimethylsiloxane diol (Dow Corning, liquid Q4-3557) is reacted with 11.7 g (0.0526 mole) of isophorone diisocyanate. After stirring under nitrogen for 5 hours at 50 ° C, the NCO content drops to 6.80% (6.90% according to theory)

Dernæst fortyndes 22,3 g af denne polydimethylsiloxandiisocyanat-præpolymer med 5,2 g (2-hydroxyethylmethacrylat (HEMA) og omrøres ved stuetemperatur under nitrogen, indtil alt NCO 25 er omsat. Den klare, methacrylat-maskerede polysiloxan opbevares koldt under nitrogen. Den består af 98,2% methacrylat--afsluttet polysiloxan og 1,8% uomsat HEMA.Next, 22.3 g of this polydimethylsiloxane diisocyanate prepolymer is diluted with 5.2 g (2-hydroxyethyl methacrylate (HEMA)) and stirred at room temperature under nitrogen until all NCO 25 is reacted. The clear methacrylate-masked polysiloxane is stored cold under nitrogen. consists of 98.2% methacrylate - completed polysiloxane and 1.8% unreacted HEMA.

Derefter fortyndes 20 g af den således fremstillede polysil-oxandimethacrylatpræpolymer med 20 g methylmethacrylat.Then 20 g of the thus-prepared polysiloxane dimethacrylate prepolymer is diluted with 20 g of methyl methacrylate.

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41 0,04 g UV-initiator A iblandes, og blandingen afgasses i vakuum. Under anvendelse af den i eksempel 2 beskrevne metode udstøbes prøver som 0,1 og 1,0 mm tykke film og plader samt i form af cylindriske skiver med en diameter på 14 mm. Den 5 klare polymer har nedenstående egenskaber: 02.DK: 8 Hårdhed ifølge Shore-D: 95 •Octan/vandkontaktvinkel: 12541 0.04 g of UV Initiator A are admixed and the mixture is degassed in vacuo. Using the method described in Example 2, samples are cast as 0.1 and 1.0 mm thick films and plates and in the form of cylindrical discs having a diameter of 14 mm. The 5 clear polymer has the following properties: 02.DK: 8 Hardness according to Shore-D: 95 • Octane / water contact angle: 125

Eksempel 71 10 På den i eksempel 1 beskrevne måde omsættes 28,98 g (0,015 mol) af en polvdimethylsiloxan-(PDMS)-polyethylen-oxid- (PEO)-blokcopolymer med strukturen PEO-PDMS-PEO, der har en ækvivalentvægt på 966 (Dow Corning, væske Q4-3667), med 6,80 g (0,0306 mol) isophorondiisocyanat (IPDI). Efter 15 omrøring under nitrogen i 1 time ved 50°C falder NCO-ind-holdet til 3,87% (3,65% ifølge teorien) (eller 0,330 ækvivalenter -NCO).Example 71 In the manner described in Example 1, 28.98 g (0.015 mole) of a poly dimethylsiloxane (PDMS) polyethylene oxide (PEO) block copolymer having the structure PEO-PDMS-PEO having an equivalent weight of 966 are reacted. (Dow Corning, liquid Q4-3667), with 6.80 g (0.0306 mole) of isophorone diisocyanate (IPDI). After stirring under nitrogen for 1 hour at 50 ° C, the NCO content drops to 3.87% (3.65% according to theory) (or 0.330 equivalents -NCO).

Dernæst blandes 28,72 g af denne NCO-maskerede præpolymer med 6,10 g (0,033 mol) tert.butylaminoethylmethacrylat (BAEM) 20 og omrøres ved stuetemperatur under nitrogen, indtil alt NCO er omsat. Reaktionens afslutning verificeres ved IR-spektro-skopi. Den klare, viskose methacrylat-maskerede PDMS-præ-polymer fortyndes med 35,2 g methylmethacrylat, og 0,14 g UV-initiator A tilsættes. Efter grundig blanding udstøbes 25 massen i form af plader og film og polymeriseres ved eksponering med ultraviolet lys.Next, 28.72 g of this NCO-masked prepolymer is mixed with 6.10 g (0.033 mol) of tert-butylaminoethyl methacrylate (BAEM) 20 and stirred at room temperature under nitrogen until all NCO is reacted. The completion of the reaction is verified by IR spectroscopy. The clear viscous methacrylate-masked PDMS prepolymer is diluted with 35.2 g of methyl methacrylate and 0.14 g of UV initiator A is added. After thorough mixing, the pulp is cast in the form of sheets and films and polymerized by exposure with ultraviolet light.

Den klare og hårde polymer består af 50% methacrylat-maske-ret polysiloxanpræpolymer og 50% methylmethacrylat. Kvældet til ligevægt indeholder den 9% vand, og den har følgende 30 oxygenpermeabilitet: 02.DK = 12.3 (9% H20); 24,3 (tør).The clear and hard polymer consists of 50% methacrylate-masked polysiloxane prepolymer and 50% methyl methacrylate. Swollen to equilibrium, it contains 9% water and has the following 30 oxygen permeability: 02.DK = 12.3 (9% H2 O); 24.3 (dry).

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Eksempel 72 På den i eksempel 1 beskrevne måde omsættes 41,0 g (0,015 mol) polydimethylsiloxan-(PDMS)-dithiol med en ækvivalentvægt på 1367 (Dow Corning X2-8024) med 6,80 g 5 (0,0306 mol) IPDI under anvendelse af 0,02 mg triethylamin som katalysator. Efter omrøring under nitrogen i 1£ time ved 24 - 28°C falder NCO-indholdet til 2,83% (2,74% ifølge teorien).Example 72 In the manner described in Example 1, 41.0 g (0.015 mole) of polydimethylsiloxane (PDMS) dithiol having an equivalent weight of 1367 (Dow Corning X2-8024) is reacted with 6.80 g (0.0306 mole) of IPDI using 0.02 mg of triethylamine as a catalyst. After stirring under nitrogen for 1 hour at 24 - 28 ° C, the NCO content drops to 2.83% (2.74% according to theory).

Dernæst blandes 44,22 g af denne NCO-maskerede præpolymer 10 med 5,96 g tert.butylaminoethylmethacrylat og omrøres ved stuetemperatur under nitrogen, indtil alt NCO er omsat. Reaktionens afslutning verificeres ved IR-spektroskopi. Den klare, viskose methacrylat-maskerede PDMS-præpolymer fortyndes med 0,5 g HEMA og 115 g methylmethacrylat, og 0,1 g UV-15 -initiator A tilsættes. Efter grundig blanding udstøbes blandingen i form af plader og film og polymeriseres ved eksponering med UV-lys.Next, 44.22 g of this NCO masked prepolymer 10 is mixed with 5.96 g of tert.butylaminoethyl methacrylate and stirred at room temperature under nitrogen until all NCO is reacted. The termination of the reaction is verified by IR spectroscopy. The clear, viscous methacrylate-masked PDMS prepolymer is diluted with 0.5 g of HEMA and 115 g of methyl methacrylate and 0.1 g of UV-15 initiator A is added. After thorough mixing, the mixture is cast in the form of sheets and films and polymerized by exposure to UV light.

Den klare polymer, der består af 69% methacrylat-maskeret polysiloxanpræpolymer, 30,7% MMA og 0,3% HEMA har følgende 20 egenskaber: 02.DK: 23The clear polymer consisting of 69% methacrylate-masked polysiloxane prepolymer, 30.7% MMA and 0.3% HEMA has the following properties: 02.DK: 23

Shore-D: 75Shore-D: 75

Octan/vandkontaktvinkel: 110Octane / water contact angle: 110

Nedenstående eksempel viser syntesen af en polymer med en 25 kædeforlænget polysiloxan.The following example shows the synthesis of a polymer with a chain-extended polysiloxane.

Eksempel 73 På den i eksempel 1 beskrevne måde omsættes 54,66 g (0,02 mol) polydimethylsiloxan-(PDMS)-dithiol med en ækvivalentvægt på 1367 (Dow Corning X8024) med 2,10 g (0,01 mol)Example 73 In the manner described in Example 1, 54.66 g (0.02 mol) of polydimethylsiloxane (PDMS) -dithiol having an equivalent weight of 1367 (Dow Corning X8024) is reacted with 2.10 g (0.01 mol)

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43 2,2,4-trimethylhexan-1,6-diisocyanat (TMDI) under anvendelse af 0,020 g triethylamin som katalysator. Efter omrøring natten over ved stuetemperatur (24°C) og under N2 viser en IR-scanning, at alle isocyanatgrupper er omsat, hvilket in-5 dikerer, at der er sket kædeforlængelse af 2 molekyler polydimethylsiloxandithiol med 1 molekyle TMDI. 56,8 g (0,01 mol) af denne kædeforlængede dithiol omsættes med 4,53 g (0,0204 mol) IPDI. Reaktionsblandingen omrøres ved 24°C i 1$ time, på hvilket tidspunkt -NCO-indholdet er 10 faldet til 1,49% (1,43% ifølge teorien). 57,2 g af denne NCO-maskerede præpolymer blandes med 3,75 g tert.butyl-aminoethylmethacrylat og omrøres ved 24°C, indtil alt NCO er omsat, hvilket bekræftes ved IR-spektroskopi.43 2,2,4-trimethylhexane-1,6-diisocyanate (TMDI) using 0.020 g of triethylamine as a catalyst. After stirring overnight at room temperature (24 ° C) and below N 2, an IR scan shows that all isocyanate groups are reacted, indicating that chain extension of 2 molecules of polydimethylsiloxane dithiol by 1 molecule of TMDI has occurred. 56.8 g (0.01 mole) of this chain-extended dithiol is reacted with 4.53 g (0.0204 mole) of IPDI. The reaction mixture is stirred at 24 ° C for 1 hour, at which time the -NCO content has decreased to 1.49% (1.43% according to theory). 57.2 g of this NCO masked prepolymer are mixed with 3.75 g of tert.butyl aminoethyl methacrylate and stirred at 24 ° C until all NCO is reacted, as confirmed by IR spectroscopy.

15 g af den methacrylat-maskerede PDMS-præpolymer blandes 15 med 35 g methylmethacrylat og 0,05 g UV-initiator A. Blandingen udstøbes i form af plader og film eller skiver polymeriseres ved eksponering med UV-lys som beskrevet i eksempel 2. Det let disede polymer har følgende egenskaber: 02.DK: 34 20 Shore-D-hårdhed: 6715 g of the methacrylate-masked PDMS prepolymer are mixed 15 with 35 g of methyl methacrylate and 0.05 g of UV initiator A. The mixture is cast in the form of plates and films or slices polymerized by exposure to UV light as described in Example 2. slightly misted polymer has the following properties: 02.DK: 34 20 Shore-D Hardness: 67

Octan/vandkontaktvinkel: 110°Octane / water contact angle: 110 °

Nedenstående eksempler illustrerer overlegenheden af polymerer indeholdende urethangrupper i forhold til polymerer, der ikke indeholder urethangrupper.The following examples illustrate the superiority of polymers containing urethane groups over polymers not containing urethane groups.

25 Eksempel 74-76Example 74-76

Polydimethylsiloxanmethacrylater, der bærer methacrylat-grupper i sidestilling til hovedkæden og bundet til denne via carbinolesterbindinger, og som kan fås fra PETRARCH Chem. Co. under kodenummeret:Polydimethylsiloxane methacrylates which carry methacrylate groups adjacent to the main chain and bonded thereto via carbinol ester linkages, which are available from PETRARCH Chem. Co. under the code number:

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4444

Eksempel_Kodenummer_Ækviva lentvægt 74 PS-486 1058 75 PS-429 2735 fortyndes til 30% med 4% HEMA og 66% cyclohexylmethacrylat.Example_Code Number_Equivalent Lent Weight 74 PS-486 1058 75 PS-429 2735 is diluted to 30% with 4% HEMA and 66% cyclohexyl methacrylate.

5 Til hver fortynding sættes 0,1% UV-initiator A, og blandingerne polymeriseres ved eksponering med UV i form af 0,1 og 1,0 mm tykke film og plader. Resultaterne er angivet i nedenstående tabel.To each dilution 0.1% UV initiator A is added and the mixtures are polymerized by exposure to UV in the form of 0.1 and 1.0 mm thick films and plates. The results are given in the table below.

Methacrylatestere, der er fremstillet ved esterificering af 10 polydimethylsiloxan-triolen (1248) med methacryloylchlorid, og som derfor ligner polysiloxanmethacrylatet ifølge eksempel 1 med undtagelse af fraværelsen af urethangrupper, giver ligeledes opake og svage polymerer, når de formuleres og polymeriseres på den ovenfor (Eks. nr. 76) beskrevne måde.Methacrylate esters prepared by esterification of the polydimethylsiloxane triol (1248) with methacryloyl chloride, and therefore similar to the polysiloxane methacrylate of Example 1, with the exception of the absence of urethane groups, also give opaque and weak polymers when formulated and polymerized above. No. 76) described.

15 Eks. nr. Udseende O2.DK Shore-DEx. No. Appearance O2.DK Shore-D

74 Uklar, skrøbelig 25 78 75 Voldsom fase-adskillelse; kan ikke måles osteagtig, dårligt poly- meriseret 76 Opak, skrøbelig; dårligt 40 polymeriseret74 Vague, fragile 25 78 75 Violent phase separation; cannot be measured cheesy, poorly polymerized 76 Opaque, fragile; poorly 40 polymerized

Nedenstående eksempel illustrerer anvendeligheden samt over-20 legenheden af hårde kontaktlinser, der er fremstillet ud fra de her omhandlede polymerer, i forhold til kendte materialer.The following example illustrates the utility as well as the superiority of hard contact lenses made from the polymers herein relative to known materials.

Eksempel 77Example 77

Runde polymerskiver ifølge eksempel 30 og 33, der er udstøbt på den i eksempel 2 beskrevne måde og har en diameter på 25 15 mm og en højde på 8 mm, fabrikeres til kontaktlinseforme ved drejning og slibning under anvendelse af konventionel teknik til fremstilling af hårde kontaktlinser. Alle prøvernes bearbejdelighed, overfladeglans, hårdhed, modstandsdygtighedRound polymer discs of Examples 30 and 33, cast in the manner described in Example 2 and having a diameter of 25 mm and a height of 8 mm, are manufactured into contact lens molds by turning and grinding using conventional techniques for the production of hard contact lenses. . All samples workability, surface gloss, hardness, resilience

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45 mod ridser samt dimensionsstabilitet og klarhed er fortrinlig, og der iagttages ingen ændring i basiskurven efter hydratise-ring.45 against scratches as well as dimensional stability and clarity are excellent and no change in the base curve after hydration is observed.

En polymerskive ifølge eksempel 30 bearbejdes til en form, 5 der passer til elektroden på et oxygenpermeabilitetsapparat. 02_Permeabiliteten måles og sammenlignes med kendte materialer, der også har god dimensionsstabilitet og udbydes som oxygenpermeable materialer til hårde kontaktlinser.A polymer disc of Example 30 is machined into a mold that fits the electrode of an oxygen permeability apparatus. 02_Permeability is measured and compared with known materials which also have good dimensional stability and are offered as oxygen permeable materials for hard contact lenses.

Materiale O2.DK Siliconeenheders struktur 10 Polymer ifølge eks. 30 27 Ifølge den foreliggende op findelseMaterial O2.GB Structure of Silicone Units 10 Polymer according to Example 30 27 According to the present invention

Polycon^ 4 Sidestillede oligosiloxan- grupper, der stammer fra oligosiloxanylalkylmeth-acrylater "SILCON"®^ 8 På siliconekautsjuk-basisPolycon ^ 4 Parallel oligosiloxane groups derived from oligosiloxanylalkylmeth acrylates "SILCON" ® ^ 8 On silicone rubber basis

Celluloseacetatbutyrat 8 Ingen silicone til stede 1) fra SYNTEX Corp.Cellulose acetate butyrate 8 No silicone present 1) from SYNTEX Corp.

15 2) Fra Dow Corning Corp.15 2) From Dow Corning Corp.

Ingen af de øvrige syntetiske fremgangsmåder til fremstilling af Si-holdige kontaktlinser producerer materialer med en så høj oxygenpermeabilitet, som kan opnås med polymerer ifølge den foreliggende opfindelse, under samtidig bevarelse af den 20 hårdhed, der er nødvendig for bearbejdning og slibning.None of the other synthetic methods for producing Si-containing contact lenses produce materials with such high oxygen permeability as can be obtained with polymers of the present invention while preserving the hardness needed for machining and grinding.

Claims (16)

1. Siliconeholdig polymer, især anvendelig til fremstil ling af kontaktlinser, kendetegnet ved, at den be-5 står af et tværbundet polymerisationsprodukt af A) fra 15 til 60 vægt-% af en lineær eller forgrenet polysiloxanraakromer med en molekylvægt fra 400 til 100.000, målt ved endegruppeanalyse eller gelpermeationskroma tograf i, hvilken makromer indeholder mindst to endestillede eller 10 sidestillede polymeriserbare olefiniske grupper for hver 5000 molekylvægtsenheder polysiloxan, idet grupperne er bundet til polysiloxanen med mindst to urethan-, thioure-than-, urinstof- eller amidbindinger, og idet makromeren har strukturen 15 ya Tb Te Td Y-X-Ri--SiO---SiO--SiO---Si-Ri-X-Y (Ai)Silicone-containing polymer, particularly useful for the production of contact lenses, characterized in that it consists of a cross-linked polymerization product of A) from 15 to 60% by weight of a linear or branched polysiloxane anchromer having a molecular weight of 400 to 100,000, measured by end group analysis or gel permeation chromatography in which macromers contain at least two terminal or 10 parallel polymerizable olefinic groups for each 5000 molecular weight units of polysiloxane, the groups being bonded to the polysiloxane with at least two urethane, thiourethane, urea or amide bonds, the macromer has the structure 15 ya Tb Te Td YX-Ri - SiO --- SiO - SiO --- Si-Ri-XY (Ai) 20 U= JX1 [if Jx2 K Jyi 25 eller 1 r i ri tg Tb Ti (R2)3—SiO--SiO---SiO--SiO---Si(Rz>3 (Az) Xl x ^ X2 35 'yz + 1 DK 165751 B hvori Rx er en lineær eller forgrenet alkylengruppe med 2-6 carbonatomer eller en polyoxyalkylengruppe med strukturen -f-CH2CHO]nCH2CH- (G) 5 R3 r3 hvori R3 er hydrogen eller methyl, og n er et helt tal på 10 1—50, R2, Ra, Rjj, Rc, R(j, Re, Rf, Rg, Rft, Rj_, Rj og R^ er methyl, x^ og x2 er hele tal fra 1 til 500, med det forbehold, at summen af x^ + x2 er 7 til 1000, y! er 0 til 14, og y2 er 1 til 13, med det forbehold, at forholdet 15 x^ + x2 Xi + x2 _ eller _ ikke er større end 70, Yl + 2 Y2 + 1 X er et diradikal med formlen 20 -Z1-CO-NH-R4-NH-CO- (C) hvori Zi betyder oxygen, svovl eller NR5, og R5 er hydrogen eller C(1-4)-alkyl, Z^ er forbundet med Rlf og R4 er det 25 divalente radikal dannet ved fjernelse af NCO-grupperne fra et aliphatisk eller cycloaliphatisk diisocyanat, Y er en gruppe med formlen -Z2-R8-Z2-CO-C==CH (D) 30 r3 r6 -Z2-CH2-C—CH2 (E) eller 35 r3 -0-R7-0-CH=CH2 (F) 40 DK 165751 B hvori Rg er hydrogen, methyl eller -C00R5, hvori R5 er hydrogen eller C(1-4)-alkyl, Z2 er oxygen eller -NR5-, R7 og Rg er lineært eller forgrenet alkylen med 2-10 carbonatomer, og fra 85 til 40 vægt-% af en vinylmonomer 5 (B) bestående af en blanding af en vandopløselig monomer B2 og en vanduopløselig monomer Blf eller en vand-uopløselig monomer Bi eller en blanding deraf, idet monomererne er monoolefiniske, eller en diolefinisk monomer Bx eller en blanding deraf, eller en blanding af de monoolefi-10 niske og diolefiniske monomerer med fra 85 til 100 vægt-% af de totale monomerer som vanduopløselige, hvor de monoolefiniske monomerer B^ er valgt blandt acrylater eller metha-crylater med formlen CH2=CR3COOR12, acrylamider eller meth-acrylamider med formlen CH2=CR3CONHRi2, maleater eller fuma-15 rater med formlen Ri2OCOCH=CHCOOR^2, itaconater med formlen R12OOCC(=CH2) CH2COOR12, vinylestere med formlen R12COOCH=CH2 eller vinylethere med formlen CH2=CHOR12, hvor R3 er hydrogen eller methyl, og R12 er en lineær eller forgrenet aliphatisk, cycloaliphatisk eller aromatisk alkylgruppe med 1-21 car-20 bonatomer, og som kan indeholde ether- eller thioether-bin-dinger eller en -CO-gruppe, eller er en heterocyclisk substitueret alkylgruppe indeholdende oxygen-, svovl- eller nitrogenatomer, eller en polypropylenoxid- eller poly-n-butylenoxidgruppe med fra 2 til 50 alkoxygentagelsesenheder, 25 eller betyder perfluorerede alkylgrupper med 1-12 carbonato-mer, eller er acylonitril, styren eller a-methylstyren, og de olefiniske monomerer B2 er valgt blandt acrylater eller methacrylater med formlen CH2=CR3COOR13, acrylamider eller methacrylamider med formlen CH2=CR3CONHR14 eller 30 CH2=CR3CON(R5)2, maleater eller fumarater med formlen R13OCOCH=CHCOOR13, vinylethere med formlen CH2=CHOR13 eller N-vinyllactamer, hvori R3 er hydrogen eller methyl, R5 er hydrogen eller c(1-4)-alkyl, R13 er en carbonhydridgruppe med 1-10 carbonatomer substitueret med en eller flere vand-35 opløseliggørende carboxy-, hydroxy- eller tert-amino-grupper, eller en polyethylenoxidgruppe med 2-100 gentagelsesenheder, DK 165751 B og R]_4 har samme betydning som R13 eller R5, og de diolefi-niske monomerer Bx er valgt blandt acrylater eller methacry-later af allylalkohol, diacrylater eller dimethacrylater af ligekædet eller forgrenet alkylenglycol med 2-6 carbonatomer, 5 af poly(ethylenoxid)glycol, af poly(propylenoxid)glycol, af poly(n-butylenoxid)glycol, af thiodiethylenglycol, af neo-pentylenglycol, af trimethylolpropan, eller af pentaerythri-tol, eller reaktionsproduktet dannet ved omsætning af 1 mol af et di- eller tri-isocyanat med formlen OCN-R4-(NCO)v, 10 hvori R4 har den ovenfor angivne betydning, og v er 1 eller 2, med 2 eller 3 mol af et hydroxyalkylacrylat eller -meth-acrylat.20 U = JX1 [if Jx2 K Jyi 25 or 1 ri ri tg Tb Ti (R2) 3 — SiO - SiO --- SiO - SiO --- Si (Rz> 3 (Az) Xl x ^ X2 35 ' yz + 1 DK 165751 B wherein Rx is a linear or branched alkylene group of 2-6 carbon atoms or a polyoxyalkylene group having the structure -f-CH2CHO] nCH2CH- (G) R3 r3 wherein R3 is hydrogen or methyl and n is an integer of 10 1 to 50, R2, Ra, Rjj, Rc, R (j, Re, Rf, Rg, Rft, Rj_, Rj and R ^ are methyl, x ^ and x2 are whole numbers from 1 to 500, with the proviso that the sum of x ^ + x2 is 7 to 1000, y! is 0 to 14, and y2 is 1 to 13, with the proviso that the ratio 15 x ^ + x2 Xi + x2 _ or _ is not greater than 70, Y1 + 2 Y2 + 1 X is a diradical of the formula 20 -Z1-CO-NH-R4-NH-CO- (C) wherein Z1 is oxygen, sulfur or NR5 and R5 is hydrogen or C (1-4) - alkyl, Z 1 is linked to R 11 and R 4 is the divalent radical formed by removal of the NCO groups from an aliphatic or cycloaliphatic diisocyanate, Y is a group of the formula -Z2-R8-Z2-CO-C == CH (D ) 30 r3 r6 -Z2-CH2-C-CH2 (E) or r3-O-R7-0-CH = CH2 (F) wherein Rg is hydrogen, methyl or -C00R5 wherein R5 is hydrogen or C (1) -4) alkyl, Z2 is oxygen or -NR5-, R7 and Rg are linear or branched alkylene of 2-10 carbon atoms, and from 85 to 40% by weight of a vinyl monomer 5 (B) consisting of a mixture of a water-soluble monomer B2 and a water-insoluble monomer Blf or a water-insoluble monomer Bi or a mixture thereof, the monomers being monoolefinic, or a diolefinic monomer Bx or a mixture thereof, or a mixture of the monoolefinic and diolefinic monomers having from 85 to 100% by weight of the total monomers as water insoluble, wherein the monoolefinic monomers B 1 are selected from acrylates or methacrylates of formula CH2 = CR3COOR12, acrylamides or methacrylamides of formula CH2 = CR3CONHRi2, maleate or fumarates of formula Ri2OCOCH = CHCOOR ^ 2, itaconates of formula R12OOCC (= CH2) CH2COOR12, vinyl esters of formula R1 2COOCH = CH 2 or vinyl ethers of the formula CH 2 = CHOR 12 wherein R 3 is hydrogen or methyl and R 12 is a linear or branched aliphatic, cycloaliphatic or aromatic alkyl group having 1-21 carbon atoms and which may contain ether or thioetherbine -dinger or a -CO group, or is a heterocyclic substituted alkyl group containing oxygen, sulfur or nitrogen atoms, or a polypropylene oxide or poly-n-butylene oxide group having from 2 to 50 alkoxy-accepting units, or meaning perfluorinated alkyl groups having 1-12 carbon atoms, or are acylonitrile, styrene or α-methylstyrene, and the olefinic monomers B2 are selected from acrylates or methacrylates of formula CH2 = CR3COOR13, acrylamides or methacrylamides of formula CH2 = CR3CONHR14 or CH2 = CR3CON (R5) 2, maleate or fumarates of formula R13OCOCH = CHCOOR13, vinyl ethers of formula CH2 = CHOR13 or N-vinyl lactams wherein R3 is hydrogen or methyl, R5 is hydrogen or c (1-4) alkyl, R13 is a hydrocarbon Riding group having 1-10 carbon atoms substituted by one or more water-solubilizing carboxy, hydroxy or tert-amino groups, or a polyethylene oxide group having 2-100 repeating units, DK 165751 B and R] 4 have the same meaning as R13 or R5 and the diolefinic monomers Bx are selected from acrylates or methacrylates of allyl alcohol, diacrylates or dimethacrylates of straight or branched chain alkylene glycol of 2-6 carbon atoms, 5 of poly (ethylene oxide) glycol, of poly (propylene oxide) glycol, of poly (n-butylene oxide) glycol, of thiodiethylene glycol, of neopentylene glycol, of trimethylolpropane, or of pentaerythritol, or the reaction product formed by reaction of 1 mole of a di- or tri-isocyanate of formula OCN-R4- (NCO) v , Wherein R4 is as defined above and v is 1 or 2, with 2 or 3 moles of a hydroxyalkyl acrylate or methacrylate. 2. Polymer ifølge krav 1, kendetegnet 15 ved, at R^ i polysiloxanen med strukturen eller A2 er alkylen med 3 eller 4 carbonatomer, x^ + x2 er fra 10 til 100, Yi er fra 0 til 2, y2 er fra 1 til 3, R4 er et diradikal af et aliphatisk eller cycoloaliphatisk diisocyanat med βίο carbonatomer, og at i gruppen med formlen (D) betyder Rg 20 hydrogen, Rg betyder ethylen, og Z2 betyder -O- eller -NC(CH3)3-.Polymer according to claim 1, characterized in that R 1 in the polysiloxane of the structure or A 2 is the alkylene of 3 or 4 carbon atoms, x 2 + x 2 is from 10 to 100, Y 1 is from 0 to 2, y 2 is from 1 to 3, R4 is a diradical of an aliphatic or cycoloaliphatic diisocyanate having βίο carbon atoms and that in the group of formula (D) R R represents hydrogen, Rg represents ethylene, and Z₂ represents -O- or -NC (CH3) 3-. 3. Polymer ifølge krav 2, kendetegnet ved, at polysiloxanen har strukturen A2/ R4 betyder diradi- 25 kalet afledt af isophorondiisocyanat, Zj og Z2 hver især betyder -0-, og y2 er 1 eller 2.Polymer according to claim 2, characterized in that the polysiloxane has the structure A2 / R4 means the direct derivative of isophorone diisocyanate, Zj and Z2 each mean -O- and y2 is 1 or 2. 4. Polymer ifølge krav 1, kendetegnet ved, at den vanduopløselige monomer er valgt blandt meth- 30 ylmethacrylat, isopropylmethacrylat, isobutylmethacrylat, tert-butylmethacrylat, isobornylmethacrylat, cyclohexyl-methacrylat, hexafluorisopropylmethacrylat og blandinger deraf. 1Polymer according to claim 1, characterized in that the water-insoluble monomer is selected from methyl methacrylate, isopropyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, isobornyl methacrylate, cyclohexyl methacrylate, hexafluoroisopropylmethacrylate and hexafluoroisopropylmethacrylate. 1 5. Polymer ifølge krav 1, kendetegnet ved, at komponent (B) indeholder 1-25% af en diolefinisk DK 165751 B monomer Bx, beregnet på den totale vægtmængde af den anvendte monomerkomponent B.Polymer according to claim 1, characterized in that component (B) contains 1-25% of a diolefinic DK 165751 B monomer Bx, based on the total weight amount of the monomer component B. used. 6. Polymer ifølge krav 1, kendetegnet 5 ved, at komponent (B) er en blanding af methylmethacrylat og 1-25 vægt%, beregnet på den samlede monomervægtmængde, neopentylenglycoldiacrylat, ethylenglycoldimethacrylat eller reaktionsproduktet af 1 mol isophorondiisocyanat og 2 mol 2-hydroxyethylmethacrylat. 10Polymer according to claim 1, characterized in that component (B) is a mixture of methyl methacrylate and 1-25% by weight, based on the total monomer weight, neopentylene glycol diacrylate, ethylene glycol dimethacrylate or the reaction product of 1 mole of isophorone diisocyanate and 2 mole of 2-hydroxyethyl. 10 7. Polymer ifølge krav 1, kendetegnet ved, at den vanduopløselige monomer Bq^ er en blanding af vinylacetat og dimethylmaleat i molforholdet 2/1 - 5/1, og methylmethacrylat, isopropylmethacrylat, isobutylmethacrylat, 15 tert-butylmethacrylat, cyclohexylmethacrylat eller hexafluor-isopropylmethacrylat eller blandinger deraf.Polymer according to claim 1, characterized in that the water-insoluble monomer Bq 1 is a mixture of vinyl acetate and dimethyl maleate in the molar ratio 2/1 - 5/1, and methyl methacrylate, isopropyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, cyclohexylmethacrylate, cyclohexyl or mixtures thereof. 8. Polymer ifølge krav 1, kendetegnet ved, at den vanduopløselige monomr Bj er valgt blandt 2- 20 ethylhexylacrylat, 2-ethylhexylmethacrylat, n-butylacrylat, n-butylmethacrylat, n-octylacrylat, n-octylmethacrylat, n-decylacrylat, n-decylmethacrylat, perfluoralkyl-c(6-l0)-substitueret alkylacrylat eller -methacrylat samt blandinger deraf. 25Polymer according to claim 1, characterized in that the water-insoluble monomer Bj is selected from 2 to 20 ethylhexyl acrylate, 2-ethylhexyl methacrylate, n-butyl acrylate, n-butyl methacrylate, n-octyl acrylate, n-octyl methacrylate, n-decyl acrylate, n-decyl acrylate , perfluoroalkyl-c (6-10) -substituted alkyl acrylate or methacrylate and mixtures thereof. 25 9. Polymer ifølge krav 1, kendetegnet ved, at den vandopløselige monomer B2 er valgt blandt 2-hydroxyethylmethacrylat, Ν,Ν-dimethylacrylamid, acrylsyre, methacrylsyre og N-vinyl-2-pyrrolidon. 30Polymer according to claim 1, characterized in that the water-soluble monomer B2 is selected from 2-hydroxyethyl methacrylate, Ν, Ν-dimethylacrylamide, acrylic acid, methacrylic acid and N-vinyl-2-pyrrolidone. 30 10 HZxRi--SiO---lio--|i0---Si-Ri ΖχΗ - 2 JX1 Y [Αί J l i*» Jyi 15 eller (R2)3SiO--|i0---feo--^i0---Si(R2> 3 (H) 20 ^ "^Xl L J Xz jy2 + 1 hvori R^, R2/ Ra/ Rb* Rc* Rd* Re> Rf* Rg/ Rh* Ri» Rj» Rk» Zlf xlf x2, Yi og y2 har de i-krav 1 angivne betydninger, 25 med diisocyanater med formlen OCN-R4-NCO hvori R4 har den i krav 1 angivne betydning, i nærværelse 30 af en katalysator, maskerer de dannede polysiloxan-polyiso-cyanat-præpolymerer i endestilling ved omsætning med et lille overskud af aktiv hydrogen-holdige monomerer med formlen10 HZxRi - SiO --- lio-- | i0 --- Si-Ri ΖχΗ - 2 JX1 Y [Αί J li * »Jyi 15 or (R2) 3SiO-- | i0 --- feo - ^ i0- - Si (R2> 3 (H) 20 ^ "^ Xl LJ Xz jy2 + 1 wherein R ^, R2 / Ra / Rb * Rc * Rd * Re> Rf * Rg / Rh * Ri» Rj »Rk» Zlf xlf x2, Y1 and y2 have the meanings specified in claim 1, with diisocyanates of the formula OCN-R4-NCO wherein R4 has the meaning given in claim 1, in the presence of a catalyst, the polysiloxane-polyisocyanate formed prepolymers in the final position by reaction with a small excess of active hydrogen-containing monomers of the formula 35 H-Z9-R0-Z9-C-C—CH II.I I o r3 r6 DK 165751 B hvori 1*3, Rg, Rg og Z2 har de i krav 1 angivne betydninger, eller med allylalkohol eller methallylalkohol eller med forbindelser med formlen 5 h2c=ch-o-r7-oh hvori R7 har den i krav 1 angivne betydning, til dannelse af polysiloxanmakromererne (A) , som man copolymeriserer med 10 en vinylmonomer (B) valgt blandt en blanding af en vandopløselig monomer B2 og en vanduopløselig monomer Bj, en vand-uopløselig monomer B^ eller en blanding deraf, idet monomererne er monoolefiniske, en diolefinisk monomer Bx eller en blanding deraf, eller en blanding af monoolefiniske monomerer 15 og diolefiniske monomerer, idet den monomere har den i krav 1 angivne betydning, under anvendelse af en initiator, som danner frie radikaler.H-Z9-R0-Z9-CC-CH II.II o r3 r6 DK 165751 B wherein 1 * 3, Rg, Rg and Z2 have the meanings given in claim 1, or with allyl alcohol or methallyl alcohol or with compounds of formula 5 h2c = ch-o-r7-oh wherein R7 is as defined in claim 1 to form the polysiloxane macromers (A) copolymerized with a vinyl monomer (B) selected from a mixture of a water-soluble monomer B2 and a water-insoluble monomer Bj, a water-insoluble monomer B 2 or a mixture thereof, the monomers being monoolefinic, a diolefinic monomer Bx or a mixture thereof, or a mixture of monoolefinic monomers 15 and diolefinic monomers, the monomer having the meaning of claim 1, using an free radical initiator. 10. Polymer ifølge krav 1, kendetegnet ved, at den indeholder (A) fra 15 til 35 vægt-% af en polysiloxanmakromer med strukturen A2, hvori R4 er diradikalet afledt af isophoron-35 diisocyanat, og Z2 hver især betyder -O-, y2 er l eller 2, og de øvrige symboler har de i krav 1 angivne betydninger, DK 165751 B og (B) fra 85 til 65 vaegt-% af en blanding af en vanduopløselig monomer (B^) , en vandopløselig monomer (B2) og en diolefinisk monomer (Bx), hvori, beregnet som vægt-% af den totale vægt 5 af monomerer, Βλ er fra 60 til 95% af en vanduopløselig monomer valgt blandt methylmethacrylat, isopropylmethacrylat, isobutylmethacrylat, tert-butylmethacrylat, cyclohexylmetha-crylat, isobornylmethacrylat og blandinger deraf, B2 er fra 15 til 0% af en vandopløselig monomer valgt blandt 2-hydr-10 oxyethylmethacrylat, Ν,Ν-dimethylacrylamid, acrylsyre, meth-acrylsyre, N-vinyl-2-pyrrolidon og blandinger deraf, og Bx er fra 25 til 5% af en diolefinisk monomer valgt blandt neopentylenglycoldiacrylat, ethylenglycoldimethacrylat og reaktionsproduktet af 1 mol isophorondiisocyanat og 2 mol 2-15 hydroxyethylmethacrylat.Polymer according to claim 1, characterized in that it contains (A) from 15 to 35% by weight of a polysiloxane macromer of structure A2, wherein R4 is diradically derived from isophorone diisocyanate and Z2 each means -O-, y2 is 1 or 2 and the other symbols have the meanings given in claim 1, DK 165751 B and (B) from 85 to 65% by weight of a mixture of a water insoluble monomer (B 1), a water soluble monomer (B2) and a diolefinic monomer (Bx) wherein, calculated as weight percent of the total weight 5 of monomers, λ is from 60 to 95% of a water-insoluble monomer selected from methyl methacrylate, isopropyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, cyclohexylmeth isobornyl methacrylate and mixtures thereof, B2 is from 15 to 0% of a water-soluble monomer selected from 2-hydroxyethyl methacrylate, Ν, Ν-dimethylacrylamide, acrylic acid, methacrylic acid, N-vinyl-2-pyrrolidone and mixtures thereof, and Bx is from 25 to 5% of a diolefinic monomer selected from neopentyl englycol diacrylate, ethylene glycol dimethacrylate and the reaction product of 1 mole of isophorone diisocyanate and 2 moles of 2-15 hydroxyethyl methacrylate. 11. Polymer ifølge krav 1, kendetegnet ved, at den består af et polymerisationsprodukt af (A) fra 40 til 60 vægt-% af polysiloxanmakromeren med struk-20 turen A2, hvori R4 er diradikalet afledt af isophorondiisocyanat, Ζχ og Z2 hver især betyder -O-, y2 er 1 eller 2, og de øvrige symboler har de i krav 1 angivne betydninger, og (B) fra 60 til 40 vægt-% af en blanding af en vanduopløselig monomer (Bi), en vandopløselig monomer (B2) og en diolefinisk 25 monomer (Bx), hvori, beregnet som vægt-% af den totale vægt af monomerer, Βχ er fra 75 til 100% af en vanduopløselig monomer valgt blandt ethylacrylat eller -methacrylat, n-butylacrylat eller -methacrylat, n-hexylacrylat eller -methacrylat, 2-ethylhexylacrylat eller -methacrylat, n-octylacry-30 lat eller -methacrylat, n-decylacrylat eller -methacrylat og blandinger deraf samt blandinger deraf med methyl- eller isobornylmethacrylat, B2 er fra 25 til 0% af en vandopløselig monomer valgt blandt 2-hydroxyethylmethacrylat, N,N-dimethyl-acrylamid, acrylsyre, methacrylsyre, N-vinyl-2-pyrrolidon 35 og blandinger deraf, og Bx er fra 5 til 0% af en diolefinisk monomer valgt blandt neopentylenglycoldiacrylat, ethylengly- DK 165751 B coldimethacrylat og reaktionsproduktet af 1 mol isophoron-diisocyanat og 2 mol 2-hydroxyethylmethylacrylat.Polymer according to claim 1, characterized in that it consists of a polymerization product of (A) from 40 to 60% by weight of the polysiloxane macromer having the structure A2, wherein R4 is diradically derived from isophorone diisocyanate, Ζχ and Z2 each mean -O-, y2 is 1 or 2 and the other symbols have the meanings given in claim 1, and (B) from 60 to 40% by weight of a mixture of a water-insoluble monomer (Bi), a water-soluble monomer (B2) and a diolefinic monomer (Bx) wherein, calculated as weight percent of the total weight of monomers, Βχ is from 75 to 100% of a water-insoluble monomer selected from ethyl acrylate or methacrylate, n-butyl acrylate or methacrylate, n hexyl acrylate or methacrylate, 2-ethylhexyl acrylate or methacrylate, n-octyl acrylate or methacrylate, n-decyl acrylate or methacrylate and mixtures thereof and mixtures thereof with methyl or isobornyl methacrylate, B2 is from 25 to 0% of a water-soluble monomer selected from 2-hydroxyethyl methacrylate, N , N-dimethyl acrylamide, acrylic acid, methacrylic acid, N-vinyl-2-pyrrolidone 35 and mixtures thereof, and Bx is from 5 to 0% of a diolefinic monomer selected from neopentylene glycol diacrylate, ethylene glycol coldimethacrylate and the reaction product of 1 mol isophorone diisocyanate and 2 moles of 2-hydroxyethyl methyl acrylate. 12. Fremgangsmåde til fremstilling af en copolymer, 5 kendetegnet ved, at man omsætter polysiloxanfor-bindelser med formlenProcess for the preparation of a copolymer, characterized by reacting polysiloxane compounds of the formula 13. Fremgangsmåde ifølge krav 12, kendete g- 20 net ved, at copolymerisationen gennemføres ved fri-radi- kalmassecopolymerisation eller i nærværelse af et opløsningsmiddel .Process according to claim 12, characterized in that the copolymerization is carried out by free-radical mass copolymerization or in the presence of a solvent. 14. Fremgangsmåde ifølge krav 13, kendete g- 25 net ved, at fri-radikalcopolymerisationen gennemføres ved indvirkning af varme eller ved bestråling.A process according to claim 13, characterized in that the free radical copolymerization is carried out by the action of heat or by irradiation. 15. Fremgangsmåde ifølge krav 14, kendeteg net ved, at varmecopolymerisationen gennemføres ved en 30 temperatur fra 40 til 105“C i nærværelse af en fri-radikal-dannende initiator.Process according to claim 14, characterized in that the heat copolymerization is carried out at a temperature of 40 to 105 ° C in the presence of a free radical-forming initiator. 16. Fremgangsmåde ifølge krav 14, kendeteg net ved, at copolymerisationen gennemføres ved UV-bestrå- 35 ling i nærværelse af en fotoinitiator.Process according to claim 14, characterized in that the copolymerization is carried out by UV irradiation in the presence of a photoinitiator.